2017 workshop « electron transfer, radical ions and radical chemistry … · 2017-03-14 · that...

ETRADCHEM Workshop 2017

23rd-24th March 2017. Villeurbanne, France

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2017 Workshop « Electron Transfer, Radical Ions and

Radical Chemistry ». March 23 and 24, 2017.

Université Lyon 1 Campus LyonTech – La Doua



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On behalf of the organizing committee, I warmly welcome you to this first Workshop edition

that will focus on electron-transfer reactions and reactivity of radical ions and radicals.

The program spans a range of topics of radical and electron-transfer processes in organic

chemistry, electrochemistry, radical and electron-transfer induced polymerization processes,

photo-electrochemistry, photoredox catalysis, catalysis and theory.

This event will honor Professor John A. Murphy (University of Strathclyde, Glasgow, Scotland)

who is an invited Professor at the Université Claude Bernard Lyon 1 from March 22 to April 20,

2017.

I would like to express my sincere thanks to all members of the organizing committee for their

continuous and enthusiastic efforts. The cellule financière of the ICBMS is also acknowledged for

their help. I am also grateful to our generous institutional and industrial sponsors, who have made

this event possible.

I wish you all a very fruitful workshop and a pleasant stay in Lyon.

Maurice MEDEBIELLE

Organizing committee: Maurice Médebielle, Lionel Perrin, Paolo Larini and Anis Tlili.

Université Claude Bernard Lyon 1, ICBMS UMR 5246.

http://www.johnmurphygroup.com/

http://www.icbms.fr/



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GENERAL INFORMATION

Location

The workshop will take place at the CPE Lyon – Ecole Supérieure de Chimie Physique

Electronique de Lyon

Locate CPE building and Tramway stations LA DOUA GASTON BERGER and UNIVERSITE

LYON 1:

http://www.cpe.fr/?lang=en

http://www.cpe.fr/?lang=en



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To access the Université Claude Bernard Lyon 1 campus (La Doua) and location of the Workshop,

please use tramway lines T1 (bound to IUT Feyssine) or T4 (bound to La Doua-Gaston Berger,

Terminus) and get off at La Doua – Gaston Berger’s station. Both lines are connected to Part Dieu

Railway Station (20-22 minutes).

From Lyon Saint-Exupéry Airport, you can reach Part Dieu Railway Station using the Rhône-

Express Train: https://www.rhonexpress.fr/en

Transport

Local public transport: http://www.tcl.fr

https://www.rhonexpress.fr/en

http://www.tcl.fr/



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Internet

Wifi access will be provided during the Workshop

Working language

The working language of the workshop is English

SPONSORS

http://www.societechimiquedefrance.fr/



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SCIENTIFIC PROGRAMME

Speakers

PLENARY LECTURE

John A. MURPHY (Glasgow, Scotland): Evolution of Organic Super Electron Donors

INVITED LECTURES

Samir ZARD (Ecole Polytechnique, Palaiseau): Radical-Polar Crossover: Manifold Implications

for Synthesis

Yannick LANDAIS (Université de Bordeaux, Bordeaux): Free-Radical Additions to Olefins.

Recent Developments and Applications

Laurence FERAY (Université d'Aix-Marseille, Marseille): α-Bromoacrylate as radical acceptor

in dialkylzincs-mediated radical-polar crossover processes, theoretical investigation and

synthetic applications

DAY 1 Thursday March 23 DAY 2 Friday March 24

8:30-9:10 Registration 8:30-8:55 Registration

9:15-9:30 Welcome 9:00-9:25 T. NOEL

9:30-10:00 J. A. MURPHY 9:30-9:55 B. KONIG

10:00-10:15 10:00-10:25 M. BRASHOLZ

10:20-10:45 S. ZARD 10:30-10:45 Break

10:50-11:15 Y. LANDAIS 10:50-11:15 M. E. BUDEN

11:20-11:45 L. FERAY 11:20-11:45 A. TLILI

11:50-12:15 C. OLLIVIER 11:50-12:15 M. PUIATTI

12:30-14:00 Lunch 12:30-14:00 Lunch

14:15-14:40 J. BROGGI 14:15-14:40 F. MASERAS

14:45-15:10 D. GIGMES 14:45-15:10 V. ROBERT

15:15-15:40 E. LACOTE 15:15-15:40 L. PERRIN

15:45-16:10 Break 15:45-16:10 Break

16:15-16:40 J. BONIN 16:15-16:45 Feedback

16:45-17:10 N. LE POUL 16:45-17:00 Farewell

17:15-17:40 C. BUCHER

17:45-18:10 M.-N. COLLOMB

19:45 Dîner


https://portail.polytechnique.edu/lso/fr/la-recherche/chimie-radicalaire/samir-zard

http://ylandais.free.fr/

http://icr-amu.cnrs.fr/spip.php?article53



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Cyril OLLIVIER (Université Pierre et Marie Curie, Paris): Photoredox Catalysis for the

Generation of Carbon Centered Radicals and Synthetic Applications

Julie BROGGI (Université d’Aix-Marseille, Marseille): New horizons for Organic Electron

Donors

Didier GIGMES (Université d’Aix-Marseille, Marseille): Photopolymerization initiators:

Synthesis and photochemical studies

Emmanuel LACOTE (Université Lyon 1, Villeurbanne): Organic and Polymer Free-radical

Synthesis using NHC–Boranes

Julien BONIN (Université Paris Diderot, Paris): Molecular Catalysis of the Photochemical

Reduction of CO2 into CO and beyond: on the Road to Solar Fuels

Nicolas Le POUL (Université de Brest, Brest): Surface functionalization by model complexes of

copper enzymes: the “self-induced electroclick” approach

Christophe BUCHER (ENS Lyon, Lyon): Electron-triggered metamorphism in viologen-based

(supra)molecular materials

Marie-Noëlle COLLOMB (Université Grenoble Alpes, Grenoble): Photo-induced redox catalysis

for hydrogen production with molecular compounds

Timothy NOEL (TU Eindhoven, Pays-Bas): Engineering of photocatalytic reactions in

microreactors

Burkhard KONIG (Université de Regensburg, Allemagne): Visible light photoredox catalysis with

radical anions

Malte BRASHOLZ (Université d'Hambourg, Allemagne): New photoredox-induced cascade

reactions

Maria Eugenia BUDEN (Université Nationale de Cordoba, Argentine): Photoinduced Electron

Transfer in base-promoted Homolytic Aromatic Substitution and Related Systems. Is t-butoxide

anion a key ingredient?

Anis TLILI (Université Lyon 1, Villeurbanne): KOtBu promoted intermolecular cross-coupling

through electron transfer

Marcelo PUIATTI (Université Nationale de Cordoba, Argentine): “The Palme d'Or goes to ...".

A search for the best functional for dealing with anionic organic species

http://www.ipcm.fr/OLLIVIER-Cyril

http://icr-amu.cnrs.fr/spip.php?rubrique19

http://icr-amu.cnrs.fr/spip.php?article17

http://lhcep.cnrs.fr/

http://www.lemp7.cnrs.fr/annuaires/FICHES/J_Bonin.htm

http://www.umr6521.cnrs.fr/membres-du-laboratoire/name/le-poul-nicolas/

http://www.ens-lyon.fr/CHIMIE/recherche/Teams/Chimie_Organique_et_Materiaux_Nanostructures/Stimuli-Responsive-Molecules-and-Materials/old-pages-2/members/faculty-members/cb

http://dcm.ujf-grenoble.fr/DCM-SITE/CIRE/index.php?page=DCM-SITE/CIRE/curriculum&Code=ccolma&labo=CIRE

http://www.noelresearchgroup.com/timothy-noel/

http://www-oc.chemie.uni-regensburg.de/koenig/

https://www.chemie.uni-hamburg.de/oc/brasholz/maltebrasholz.html

http://www.conicet.gov.ar/new_scp/detalle.php?id=26038&datos_academicos=yes

http://fmi-lyon.bcpmdb.com/Effectifs/ATlili/index.html

http://infiqc.fcq.unc.edu.ar/index.php?controller=render&action=personal&idCat=11&idPersonal=72



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Feliu MASERAS (Tarragone, ICIQ, Catalogne): Characterization of single electron steps in water

oxidation through DFT calculations

Vincent ROBERT (Université de Strasbourg, Strasbourg): Charge Transfer Processes: Prime

Role of Optimized Molecular Orbitals

Lionel PERRIN (Université Lyon 1, Villeurbanne): Exploring the reactivity of the Kagan’s

reagent from a theoretical perspective

http://www.iciq.org/research/research_group/prof-feliu-maseras/

https://quantique.u-strasbg.fr/doku.php?id=fr:pageperso:vr:welcome

http://www.icbms.fr/itemm



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Evolution of Organic Super Electron Donors

J. A. Murphy

Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL,

United Kingdom

* [email protected]

My research group has been fortunate to develop a number of simple organic electron donors,

structurally related to enols, enolates and enamines; in this way, we have built upon the excellent

pioneering work of many people including Bunnett,1 Rossi2 and Narasaka.3

Our starting point was to ask whether a neutral organic ground state molecule could reduce an aryl

halide. The search for such a molecule led us to understand some of the factors that control the

power and selectivity of organic electron donors, and their scope as reducing agents.

Being coloured reagents, they readily absorb visible and near-UV light; this adds to their power as

donors, and allows them to tackle even more challenging synthetic tasks. This presentation will

give an overview of developments relating to these electron donors from our current perspective.

References

1. Scamehorn, R. G.; Bunnett, J. F. J. Org. Chem. 1977, 42, 14491457.

2. Guastavino, J. V.; Rossi, R. A. J. Org. Chem. 2012, 77, 460472.

3. Narasaka, K. Pure & Appl. Chem. 1997, 69, 601604.

-1,50E-05

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5,00E-06

1,00E-05

-2,5 -2 -1,5 -1 -0,5 0

Cu

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Potential/ V



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Professor JOHN A. MURPHY

B.A. (Mod.), Ph.D., C. Chem., F.R.S.C., F.R.S.E.

CURRICULUM VITAE


1. Name: John Anthony Murphy Nationality: Irish

2. University Education:

1972-1976 University of Dublin.

Awarded B.A. (Moderatorship) First Class.

Awards Held: Department of Education Scholar (1972-1976).

University of Dublin Foundation Scholar (1974-1979). Goulding Scholar

(1975); Gold Medallist of the University (1976); Cocker Medallist for

Experimental Chemistry (1976).

1976-1979 University of Cambridge. (Hutchinson Research Studentship.)

Awarded Ph.D. in Organic Chemistry (with Prof. Jim Staunton)

3. Appointments Held:

2013-2016 Head of Department

2007-2012 Director, Glasgow Centre for Physical Organic Chemistry

2010- to date Head of Organic Chemistry

2007-2013 Deputy Head of Department

2006-2008 Director, WestCHEM

2004-2006 Deputy Director, WestCHEM

1995- to date Merck-Pauson Professor, University of Strathclyde.

1994-1995 Reader, University of Nottingham.

1983-1994 Lecturer, University of Nottingham.

1982-1983 College Lecturer, Jesus College, Oxford. .

1980-1983 Departmental Demonstrator, University of Oxford.

with Prof. J. E. Baldwin on bioorganic chemistry.

1979-1980 Izaak Walton Killam Fellowship, University of Alberta

4. International and National Recognition:

2017 Visiting Professor, Université Claude Bernard (Lyon- 1)

2016 The Charles Rees Award for Heterocyclic Chemistry (Royal Society of

Chemistry)

2013 Visiting Lectureship, University of Kyoto

2012 The Bader Award in Organic Chemistry (Royal Society of Chemistry)

2007 Visiting Fellow at the Australian National University.

2004 Visiting Professor, Université Pierre et Marie Curie, Paris




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2002 D.Sc. (University of Strathclyde)

2001 Presidential Visiting Professor, N.A.I.S.T., Japan.

2001 Elected Fellow of the Royal Society of Edinburgh

2001 Royal Society Leverhulme Senior Research Fellow

1999 Invited “Troisième Cycle” Lecturer, Switzerland.

1998 Elected Fellow of the Royal Society of Chemistry.

1996 Visiting Professor at l’Université d’Aix Marseille.

1995 Visiting Fellow at the Australian National University.

I am an organic chemist and my research group revels in exploring chemical reactivity in synthesis

and in biology. My research group website is http://www.johnmurphygroup.com/ We have a

particular interest in electron transfer reactions and in radical chemistry, but are generally interested

in mechanisms of organic reactions.




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Radical-Polar Crossover: Manifold Implications for Synthesis

S. Z. Zard

Laboratoire de Synthèse Organique, Ecole Polytechnique, 91128 Palaiseau, France.

[email protected]

Abstract. Our research group is mostly concerned with the discovery and development of new

reactions and processes that could be useful in organic synthesis. As is usually the case in scientific

research, the interplay between conjecture and chance observation underlies much of our work.

Unexpected events often bring a fresh lighting to the system being examined and open doors

hitherto unsuspected. Misconception has thus played an important role by allowing us to uncover

a number of new radical and non-radical reactions of some generality involving sulfur compounds,

acetylenes, oximes, and related derivatives: we simply followed the logical consequences of our

observations and went where the chemistry took us. In this lecture, the crossover from the radical

to the cationic manifold that can take place in some of these reactions will be presented and the

various mechanistic and synthetic implications discussed briefly.



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Samir Z. Zard

Personal: Date and place of birth: 18th June 1955, Ife (Nigeria)

Nationality: French Marital status: Married, two children

Professional Address: Laboratoire de Synthèse Organique, Ecole Polytechnique, 91128 Palaiseau,

France.

Phone: +33-1-69 33 59 71; Fax: +33-1-69 33 59 72; e-mail: [email protected]

Education:

1978 BSc : Imperial College of Science and Technology, London University (1st Class Honours).

ARCS (Associate of the Royal College of Science) 1st Class Honours.

Awards: Hofmann Prize; Edward Frankland Prize; Edmund White Prize

1983 PhD : Université Paris-Sud, Orsay, France (supervisor: Professor Sir Derek Barton).

Employment:

CNRS: 1981, Attaché de Recherche; 1983, Chargé de Recherche; 1989, Directeur de Recherche (2nd

Class); 1996, Directeur de Recherche (1st Class); 2003, Directeur de Recherche (Exceptional Class).

Ecole Polytechnique: 1986, Maître de Conférences (part- time); 2000, Full Professor (part-time).

Field of research: Discovery and mechanistic study of new reactions and processes.

Publications: 342; Patents: 37

Honors and distinctions:

* The 1992 Prize of the Organic Chemistry Division of the French Chemical Society.

* The 1995 Clavel-Lespiau Prize of the French Academy of Science.

* Chemistry Research Promotion Center of the National Science Council Fellow (Taiwan, 1997)

* Astra-Zeneca USA Lecturer 1999.

* Sherbrooke-Bohringer Ingelheim Canada Lecturer 2000

* Rhodia Prize 2000

* Bürgenstock Lecturer 2001

* Merck Sharpe & Dohme Lecturer 2003

* Chevalier des Palmes Académiques 2003

* Japan Society for the Promotion of Science Fellow 2004.

* Organic Syntheses Distinguished Lecturer 2005

* Novartis Chemistry Lectureship 2006-2007

* Inaugural Wyeth Lecturer 2006

* Prix Dargelos 2006

* President, Bürgenstock Conference 2007

* Silver Medal CNRS 2007

* Croix de Chevalier dans l’Ordre de la Légion d’Honneur 2007

* Novartis-UC Irvine Distinguished Lecturer 2008

* Novartis-Berkeley Distinguished Lecturer 2008

* Bristol-Myers Squibb-Scripps Institute Distinguished Lecturer 2008

* Prix de l’Innovation 2008 — Ecole Polytechnique

* Grignard-Wittig Award 2008 of the German Chemical Society



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* Woodward Lecturer, Harvard University 2010

* Bohringer Ingelheim-University of British Columbia Distinguished Lecturer 2010-2011

* Honorary Member of the Sociedad Argentina de Investigación en Química Orgánica, 2011

* Fellow of the Royal Society of Chemistry, 2011

* 1st Barton Lecturer in Creativity in Organic Synthesis (2012-Imperial College)

* Grand Prix Joseph-Achille Le Bel of the French Chemical Society, 2012

* Birch Lecturer, Australia National University, 2015

* Liversidge Lecturer, University of Sydney, 2015

* Elected Foreign Corresponding Member of the Academy of Sciences of Lisbon (Portugal), 2015

* Honorary Doctorate, American University of Beirut, 2016.



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Free-Radical Additions to Olefins. Recent Developments and Applications

Y. Landaisa

a Institute of Molecular Sciences, University of Bordeaux, UMR-CNRS-5255, 351 cours de la libération, 33405

Talence, France

* [email protected]

The regioselective free-radical addition onto olefins has attracted a considerable interest as it gives

rise to useful intermediates for organic synthesis starting from readily available material.1 In this

context, our laboratory has developed three-component radical functionalization of olefins, relying

on the addition of two carbon fragments across the olefinic skeleton, providing adducts with two

new C-C bonds along with additional functional groups. Carbo-alkynylation and carbo-oximation

as well as carbo-aminomethylation were thus devised, using various olefinic partners and sulfones

as radical traps.2 More recently, we extended this chemistry to the development of a one-pot carbo-

alkenylation of olefins,3 as well as a useful carbo-cyanation.4 The scope and limitations of these

methodologies will be discussed, along with their application to the total synthesis of natural

alkaloids.5 Efforts towards the development of tin-free versions of these processes will also be

disclosed.

(1) Subramanian, H.; Landais, Y.; Sibi M. P. in Comprehensive Organic synthesis, Eds. G. A. Molander, P. Knochel,

2nd ed., Vol. 4, Oxford: Elsevier, 2014, pp. 699-741.

(2) (a) Godineau, E.; Landais, Y. J. Am. Chem. Soc. 2007, 129, 12662. (b) Liautard, V.; Robert, F.; Landais, Y. Org.

Lett. 2011, 13, 2658. (c) Ovadia, B.; Robert, F.; Landais, Y. Org. Lett. 2015, 17, 1958. (d) Landais, Y.; Robert,

F.; Godineau, E.; Huet, L.; Likhite, N. Tetrahedron 2013, 69, 10073. (e) Ovadia, B.; Robert, F.; Landais, Y.

Chimia, 2016, 70, 34.

(3) (a) Poittevin, C.; Liautard, V.; Beniazza, R.; Robert, F.; Landais, Y. Org. Lett. 2013, 15, 2814. (b) Beniazza, R.;

Liautard, V.; Poittevin, C.; Ovadia, B.; Mohammed, S.; Robert, F.; Landais, Y. Chem. Eur. J. 2017, 23, 2439.

(4) (a) Hassan, H.; Pirenne, V.; Wissing, M.; Chahinaz, K.; Hussain, A.; Robert, F.; Landais Y. Chem. Eur. J. 2017,

DOI: 10.1002/chem.201605946. (b) Dange, N. S.; Robert, F.; Landais, Y. Org. Lett. 2016, 18, 6156.

(5) Hassan, H.; Mohammed, S.; Robert, F.; Landais, Y. Org. Lett. 2015, 17, 4518.



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Prof. Yannick Landais Institute of Molecular Sciences (UMR-5255), University of Bordeaux 351, Cours de la libération, 33405 Talence, France Tel: (+33) 5 40 00 22 89; Fax: (+33) 5 40 00 62 86 Email: [email protected]

A. Personal Information Date of Birth: 09.01.1962 Place of Birth: Angers, France

B. Higher education and professional experience 1997- Professor of Organic Chemistry at the University of Bordeaux (F) 1990-97 Assistant-Professor (University of Lausanne, CH). 1994 Habilitation (University Paris-XI, Orsay, F). 1988-90 Postdoctoral fellow at the University of Cambridge (UK) with Prof. I. Fleming 1987-88 Military Service 1984-87 PhD thesis with Dr. J.-P. Robin, University Paris-XI-Orsay (F). "Recherche sur les voies d’accès aux

lignanes bisbenzocyclooctadiénes et aux alcaloïdes présentant la structure biarylique pontée".

C. Fellowships, Awards and Honors 2014 Prize of the Organic Chemistry Division of the French Chemical Society (http://www.societechimiquedefrance.fr/Chimie-organique-14.html) 2014 Fellow of the French Chemical Society (1st promotion) 2000-05 Junior Member of the "Institut Universitaire de France" 1997 Alfred Werner Prize of the New Swiss Chemical Society (https://scg.ch/award) 1988-90 EU Postdoctoral Fellowship (Cambridge, UK) 1984-87 PhD Fellowship from the French “Ministère de la Recherche et de l’Enseignement Supérieur“

D. Research Interests Organosilicon Chemistry, Radical and organometallic chemistry, Organocatalysis, Asymmetric synthesis, Synthesis of natural products. See also webpage: http://ylandais.free.fr

E. Metrics 127 publications in peer-reviewed journals, 10 book chapters, 2 patents.

F. Lectures in Universities and industries 70 lectures in universities 28 Lectures in national and international congresses.

G. Selected Administrative duties

2010-14 Member of the Scientific committee of the CNRS National Institute of Chemistry (INC) 2013- President of the French-Japanese Association of Chemistry 2015- Member of the International Advisory Board of “European Journal of Organic Chemistry”

H. Supervision

Supervision of 30 PhD thesis, 5 currently ongoing, and 13 post-doctoral researchers.

mailto:[email protected]

http://www.societechimiquedefrance.fr/Chimie-organique-14.html

https://scg.ch/award

http://ylandais.free.fr/



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α-Bromoacrylate as radical acceptor in dialkylzincs-mediated radical-polar

crossover processes, theoretical investigation and synthetic applications.

Laurence Feray,* Hugo Lingua, François Vibert, Julien Maury, Eric Besson, Didier Siri and

Michèle P. Bertrand

Aix Marseille Univ., CNRS, Institut de Chimie Radicalaire, UMR 7273, Equipes CMO and CT, Campus Saint-

Jérôme, Avenue Normandie-Niemen, 13397 Marseille Cedex 20, France

*[email protected]

Under non-degassed medium ethyl -bromoacrylate reacts with diethylzinc to give a

bromocyclopropane. The reaction successively involves a radical addition followed by an SH2 at

zinc, conjugate addition of the resulting enolate to the electrophilic substrate and finally a ring

closure.[1] In the presence of t-butyl iodide the bromocyclopropane resulting from the addition of

t-butyl radical is formed.

Theoretical calculations were performed to get a better insight into the detailed mechanism. They

highlight the impact of zinc(II) chelation on the formal SH2 step.

[1] Vibert, F; Maury, J; Lingua, H; Besson, E; Siri, D; Bertrand, M.P.; Feray, L. Tetrahedron 2015, 71, 8991–9002



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Feray Laurence Professeur des Universités

Aix-Marseille Université, Institut de Chimie Radicalaire

Equipe CMO, Campus Saint-Jérôme, case 562, Marseille

33 (0)4 91 28 85 99 / 06 17 37 52 03

[email protected]

Education and scientific career

1996-2000 Ph. D. in Organic Chemistry under the direction of Pr Michèle Bertrand, Marseille. Thematic area:

Triethylborane and diethylzinc in radical reactions.

2000-2001 Post-doctoral position under the direction of Pr Philippe Renaud, Fribourg, Switzerland.

Thematic area : Diastereoselective 1,5-hydrogen atom transfer.

2001 Maître de conférences, Aix-Marseille Université (AMU)

2008 Habilitation à Diriger des Recherches (HDR), Marseille « Dialkylzincs in radical chemistry, synthetic

applications »

2015 Professeur, Aix-Marseille Université

Research :

Development of radical methodologies based on the use of organometallic reagents.

Dialkylzincs as promoters of radical-polar multicomponent reactions in aerobic medium, mechanistic studies and

synthetic applications (synthesis of -lactones, lactams, pyrrolizidines, stereocontrolled synthesis of olefines…)

Metal catalyzed carbozincation of various substrates

Training and administrative responsabilities in Aix-Marseille Université:

Manager of L2, L3 chemistry degree

Assistant Director, departement of chemistry

Keywords:

Radical chemistry, Organometallic chemistry, Dialkylzincs, Radical-polar cascades, Multicomponent reactions.

Selected recent publications

(a) J. Maury, L. Feray, P. Perfetti, M. P. Bertrand, Org. Lett. 12 (2010) 3590. (b) J. Maury, D. Mouysset, L. Feray, S.

R. A. Marque, D. Siri, M. P Bertrand, Chem. —Eur. J. 18 (2012) 3241. (c) J. Maury, L. Feray, M. P Bertrand, Org.

Lett. 13 (2011) 1884. (d) J. Maury, S. Jammi, F. Vibert, S. R. A. Marque, D. Siri, L. Feray, M. P. Bertrand, J. Org.

Chem. 77 (2012) 9081. (e) S. Jammi, D. Mouysset, D. Siri, M. P Bertrand, L. Feray, J. Org. Chem. 77 (2013) 1589.

(f) Vibert, F.; Maury, J.; Lingua, H.; Besson, E.; Siri, D.; Bertrand, M. P.; Feray, L. Tetrahedron 2015, 71, 8991-9002.



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Photoredox Catalysis for the Generation of Carbon Centered Radicals

and Synthetic Applications

C. Ollivier

UPMC Univ-Paris 06 – Sorbonne Universités, Institut Parisien de Chimie Moléculaire (UMR CNRS 8232)

4 Place Jussieu, C. 229, 75005 Paris, France

[email protected]

Visible-light photoredox catalysis has emerged as a valuable and a greener alternative to generate

radicals by single electron transfer reactions from an appropriate photocatalyst - which can be a

polypyridine complex of transition metal or an organic dye - that absorbs light in the visible region.

Since the pioneering studies of Kellogg, Pall and Deronzier, important contributions have been

reported for synthetic purposes. In this context, we investigated various radical transformations1

involving photoreduction of ketoepoxides, ketoaziridines, onium salts and O-thiocarbamates. We

took advantage of the reactivity of the photogenerated radicals to create new carbon-carbon bonds

and related mechanistic studies were performed. Our next endeavors concerned the photocatalyzed

oxidation of stabilized carbanions such 1,3-dicarbonyl enolates and more extensively bis-

catecholato silicates. Because of their low oxidation potentials, the later have proved to be exquisite

sources of radical entities which can be engaged in diverse intermolecular reactions such as

vinylation, alkynylation and conjugate additions. The bis-catecholato silicates were also shown to

behave as excellent partners of dual photoredox-nickel dual catalysis leading in an expeditious

manner to libraries of cross coupling products.

1 For an account of this work, see: Goddard, J.-P.; Ollivier, C.; Fensterbank, L. Acc. Chem. Res. 2016, 49, 1924.



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Cyril OLLIVIER

CNRS Research Director

PhD and Habilitation Diploma (HDR) in Organic Chemistry

Université Pierre et Marie Curie – Sorbonne Universités, Institut Parisien de Chimie Moléculaire (UMR 8232), 4, Place Jussieu. Case 229. Tour 32-42, 5ème étage, pièce 516, 75252 Paris Cedex 05. France

Tel. ++33 (0)1 44 27 38 50 Fax ++33 (0)1 44 27 73 60, [email protected] http://www.ipcm.fr/OLLIVIER-Cyril

EDUCATION AND DIPLOMAS Habilitation Diploma (HDR) – Accreditation to supervise research June 2013 Pierre and Marie Curie University – Sorbonne University, Paris, France Ph.D. in Organic Chemistry - Doctor rerum naturalium December 2000 joint degree at the University of Fribourg, Fribourg, Switzerland and Pierre and Marie Curie University, Paris, France Thesis Title: Development of efficient and practical radical processes for the formation of carbon-carbon and carbon-heteroatom bonds B.S.; M.S. in Chemistry June 1995 Pierre and Marie Curie University, Paris, France Research Interests in Master: Reactivity of hemithioketals as carbenoïds in 1,2 metallate rearrangement

CURRENT POSITION Pierre and Marie Curie University – Sorbonne University, Paris, France October 2016 – present CNRS Research Director Research Interests: Development of new directions for research on synthetic radical and organometallic chemistry

PREVIOUS POSITIONS Pierre and Marie Curie University, Paris, France January 2007 – September 2016 CNRS Research Fellow 1st class (Chargé de recherche) Research Interests: Development of new directions for research on synthetic radical and organometallic chemistry Aix-Marseille University, Marseille, France October 2002 – December 2006 CNRS Research Fellow 2nd class (then 1st class in October 2006) Research Interests: Reactivity of allylsilanes and synthesis of steroids, particularly vitamin D analogs University of Texas at Austin, Austin, TX January 2001 – September 2002



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SNSF and NIH Postdoctoral fellow Advisor: Prof. Philip D. Magnus Research Interests: Approaches to the total synthesis of the diterpene antibiotic guanastepene University of Fribourg, Fribourg, Switzerland October 1996 – December 2000 and Pierre and Marie Curie University, Paris, France Graduate Student (Swiss National Science Foundation (SNSF)) Advisors: Prof. Philippe Renaud and Prof. Max Malacria Research Interests: Organoboranes as a source of radicals, radical oxygenation and azidation Ecole Nationale Supérieure de Techniques Avancées, Paris, France October 1995 – September 1996 Scientific Associate in Organic Chemistry Advisor: Cmdr. Dr. Laurent El Kaim Research Interests: Diazo esters addition to trifluoropyruvamides Pierre and Marie Curie University, Paris, France October 1994 – June 1995 Master Student Advisors: Prof. Jean-François Normant and Dr. Fabrice Chemla Research Interests: Reactivity of hemithioketals as carbenoïds in 1,2 metallate rearrangement

CURRENT RESEARCH INTERESTS Organic Synthesis Methods and Concepts. Radical Synthetic Chemistry. Organometallic Catalysis for Synthesis. Asymmetric catalysis. Eco-friendly Synthesis. Multi-step Synthesis Green Radical Synthesis: Methods and Development of New Cascade Processes ➢ N−Acylcyanamides as new partners for radical cascade reactions. Synthesis of polyheterocyclic

nitrogen-containing compounds ➢ Electron Transfert Reactions

• Use of Titanium(IV) and Iron(II) complexes as new radical mediators • Development of visible-light photoredox catalysis for the generation of radicals

Transition metal catalyzed cyclization and cycloisomerisation ➢ Chiral counteranions in asymmetric catalysis

PUBLICATIONS AND BIBLIOMETRIC DATA 70 Research publications 7 Book chapters 15 International and national lectures, seminars and oral communications 35 Posters



22

New horizons for Organic Electron Donors

J. Broggi*

Aix Marseille Univ, CNRS, ICR Institut de Chimie Radicalaire, Faculté de Pharmacie, Marseille, France

*[email protected]

The astonishing recent advances of their reactivities in fundamental organic chemistry have raised

a real interest for reducing agents with totally organic neutral structures and exceptionally negative

redox potentials.1 Strong organic electron donors (OEDs) are capable of single- or double-electron

transfer to organic substrates under mild and homogeneous conditions, promoting bond formations

through the generation of radical or anionic intermediates. Major contributions have been made in

this field demonstrating the efficiency of OEDs in the selective reduction of challenging chemical

bonds.2 The OEDs thus represent serious rivals to highly aggressive metal-based reducers and

emerge as an attractive novel source of reducing electrons in many aspects.

Despite a great tunability, approaches involving OED-promoted electron transfers have been

under-exploited, limiting the visibility of academic and industrial applications. Their convenience

of manipulation and storage is still hampered by several technical parameters that could dissuade

chemists of their usage. In order to extend their functionalities, our research primarily focus on the

development of new methodologies, essential to outline the potential of organic electron donors.

Our recent results in the development of masked OED-systems and the exploration of

unprecedented applications in the field of material science will be presented.3

1For reviews, see: a) Broggi, J.; Terme, T.; Vanelle, P. Angew. Chem. Int. Ed. 2014, 53, 384. b) Murphy, J. A. In

Encyclopedia of Radicals in Chemistry, Biology and Materials; Chatgilialoglu, C., Studer, A., Eds.; WILEY-VCH,

Weinheim, 2012. c) Zhou, S.; Farwaha, H.; Murphy, J. A. Chimia 2012, 66, 418. d) Murphy, J. A. J. Org. Chem. 2014,

79, 3731. e) Doni, E.; Murphy, J. A. Chem. Commun. 2014, 50, 6073. 2 a) Cahard, E.; Schoenebeck, F.; Garnier, J.; Cutulic, S. P. Y.; Zhou, S.; Murphy, J. A. Angew. Chem., Int. Ed. 2012,

51, 3673. b) Farwaha, H. S.; Bucher, G.; Murphy, J. A. Org. Biomol. Chem. 2013, 11, 8073. c) Doni, E.; O’Sullivan,

S.; Murphy, J. A. Angew. Chem. Int. Ed. 2013, 52, 2239. d) Doni, E.; Mondal, B.; O’Sullivan, S.; Tuttle, T.; Murphy,

J. A. J. Am. Chem. Soc. 2013, 135, 10934. e) Hanson, S. S.; Richard, N. A.; Dyker, C. A. Chem. Eur. J. 2015, 21, 8052.

f) Hanson, S. S.; Doni, E.; Traboulsee, K. T.; Coulthard, G.; Murphy, J. A.; Dyker, C. A. Angew. Chem. Int. Ed. 2015,

54, 11236. 3 Broggi, J.; Rollet, M.; Clément, J.L.; Canard, G.; Terme, T.; Gigmes, D.; Vanelle P. Angew. Chem. Int. Ed. 2016,

55, 5994. b) Rayala, R.; Giuglio-Tonolo, A.; Broggi, J.; Terme, T.; Vanelle, P.; Theard, P.; Médebielle, M.; Wnuk, S. F.

Tetrahedron 2016, 72, 1969.



23

BROGGI Julie

Born: June 6th 1982

in Cannes, Alpes Maritimes

Nationality: French Current Position

Maître de Conférences (Lecturer) at the Organic Chemistry Department (Faculty of Pharmacy, AMU)

Institut de Chimie Radicalaire (ICR) - UMR 7273, Equipe Pharmacochimie radicalaire (PCR), 27 Bd Jean

Moulin, 13385 Marseille Cedex 5.

+33 (0)4 9183 5996 / [email protected]

Professional Experience

2010-2011 ATER (teaching assistant) - Laboratoire Chimie Provence (LCP), UMR 6264, Faculty of

Pharmacy, Aix-Marseille II.

Title: Super Electron Donors as tools in the synthesis of new nucleosidic analogues.

2009 Post-doctoral position – S. P. Nolan group Research school of chemistry, St Andrews,

United Kingdom.

Title: European project (EuMet): Development and application in catalysis of ruthenium

complexes bearing an N-heterocyclic carbene.

2005-2008 Ph.D. - Institut de Chimie Organique et Analytique (ICOA), UMR 6005, Faculty of

Science, Orléans.

Title: Contribution of N-heterocyclic carbene-containing catalysts in the nucleoside

chemistry. (Advisor: Prof. L.A. Agrofoglio and Dr. S. Bertaina-Raboin)

2005 Master training course - Laboratoire de Chimie des Molécules BioActives et des Arômes

(LCMBA), UMR 6001, Faculty of Science, Nice.

Title: Synthesis of a new AZT prodrug.

Research interests

JB is involved in the synthesis of novel organic reducers and their stable latent precursors. She also explores

their reactivity in the reduction of uninvestigated species and for unprecedented applications including

nucleoside or polymer chemistry. She is experienced in organic and medicinal compound synthesis, as well

as coordination chemistry and organometallic catalysis. She is used to perform air- and moisture-sensitive

experiments and handle unstable products.

Scientific Publications

19 publications in peer-review journals including 3 contributions to monographs, 3 oral communications

and 18 poster presentations.

• Polymerization initiated by organic electron donors J. Broggi,* M. Rollet, J.-L. Clément, G. Canard, T. Terme, D. Gigmes, P. Vanelle* Angew. Chem. Int. Ed.

2016, 55, 5994-5999.

• Studies toward the oxidative and reductive activation of C-S bonds in 2'-S-aryl-2'-thiouridine

derivatives R. Rayala, A. Giuglio-Tonolo, J. Broggi, T. Terme, P. Vanelle, P. Theard, M. Médebielle,* S. F. Wnuk*

Tetrahedron, 2016, 72, 1969-1977.

• Organic electron donors as powerful single-electron reducing agents in organic synthesis



24

J. Broggi,* T. Terme,* P. Vanelle* Angew. Chem. Int. Ed. 2014, 53, 384-413.

• The isolation of [Pd{OC(O)H}(H)(NHC)(PR3)] (NHC = N-heterocyclic carbene) and its role in alkene

and alkyne reductions using formic acid

J. Broggi, V. Jurcík, O. Songis A. Poater, L. Cavallo, A. M. Z. Slawin, C. S. J. Cazin*J. Am. Chem. Soc.

2013, 135, 4588-4591.

• Novel antiviral C5-substituted pyrimidine acyclic nucleoside phosphonates selected as human

thymidylate kinase substrates D. Topalis, U. Pradère, V. Roy, C. Caillat, A. Azzouzi, J. Broggi, R. Snoeck, G. Andrei, J. Lin, S. Eriksson,

J. A. C. Alexandre, C. El-Amri, D. Deville-Bonne, P. Meyer, J. Balzarini, L. A. Agrofoglio* J. Med. Chem.

2011, 54, 222-232.

Julie Broggi, received her M.Sc. in organic chemistry from the Université de Nice Sophia-Antipolis

(France) in 2005 and then completed her Ph.D. on nucleoside chemistry in 2009 under the supervision of

Prof. Luigi Agrofoglio at the Université d’Orléans (France). Her Ph.D. work focused on the applications of

transition-metal complexes in the synthesis of nucleoside derivatives, such as triazolo-carbanucleosides and

phosphononucleosides. These potential smallpox inhibitors were synthesized in racemic or enantioselective

series. During this Ph.D., she spent some time as visiting fellow in the group of Prof. Steven P. Nolan at the

Institute of Chemical Research of Catalonia (Spain). She studied the contribution of copper and palladium

complexes, bearing N-heterocyclic carbene ligand, in cycloaddition, N-arylation or transfer hydrogenation

reactions. For the study of their mechanism of action, she used NMR spectroscopy at variable temperature

and isotopic-labelling experiments.

Early 2009, she moved to the School of Chemistry of the University of St Andrews (UK) to continue

working with Prof. Nolan as post-doctoral fellow. She worked on the synthesis of imidazolium salts and the

corresponding free carbenes along with the synthesis of ruthenium catalysts and their applications in

metathesis reactions. In the context of a metathesis European network (project EUMET - CP-FP 211468-

2), she supervised the training of junior group members.

In 2010, she was appointed ATER and then Maître de Conférences (Lecturer) in the PCR group of the

Institut de Chimie Radicalaire (ICR). She is involved in the synthesis of novel organic electron donors

and their stable latent precursors. These new organic reducers are used as powerful and selective alternative

tools to metallic derivatives in reduction strategies through single- or double-electron transfers. she also

explores their reactivity in the reduction of uninvestigated functional groups and for unprecedented

applications including nucleoside or polymer chemistry.



25

Photopolymerization initiators: Synthesis and photochemical studies

D. Gigmes

Aix Marseille Univ, CNRS, Institut de Chimie Radicalaire, Marseille, France

[email protected]

Nowadays, photoinitiated polymerization is one of the preferred techniques for a large range of

applications such as coatings, inks and adhesives, dentistry, microelectronics, laser direct imaging

technology and 3D printing.1-3 Indeed, photopolymerization presents several advantages such as

fast polymerization kinetics even at room temperature, the absence of solvents limiting the

formation of volatile organic compounds and the possibility to irradiate with high precision specific

zones allowing the construction of tailored patterns. However, the employment of UV light,

generally required for this technique, remains a major issue due to its high energy and the toxicity

of the associated irradiation sources. To overcome this drawback, photoinitiating systems able to

initiate polymerization under soft light irradiation sources is currently the subject of intense

efforts.3 In this context, recently we have synthesized a large library of photosensitive molecules

based on naphthalimide and diketopyrrolopyrrole derivatives exhibiting for some of them a

remarkable effiency to initiate the polymerization under soft irradiation sources.4,5 Hence, in this

communication, the synthesis and the polymerization abilities of the most relevant prepared

compounds as well as their photochemical behaviour will be presented.

References

1. Fouassier, J. P.; Lalevee, J. Photoinitiators for Polymer Synthesis: Scope, Reactivity and Efficiency; Wiley-VCH:

Weinheim, Germany, 2012.

2. Dadashi-Silab, S.; Doran, S.; Yagci, Y. Chem. Rev. 2016, 116, 10212–10275.

3. Xiao, P.; Zhang, J.; Dumur, F.; Tehfe, M. A.; Morlet-Savary, F.; Graff, B.; Gigmes, D.; Fouassier, J. P.; Lalevée,

J. Prog. Polym. Sci. 2015, 41, 32-66.

4. Zhang, J.; Zivic, N.; Dumur, F.; Xiao, P.; Graff, B.; Fouassier, J. P.; Gigmes, D.; Lalevée, J. Polymer, 2014, 55,

6641-6972.

5. Zivic, N.; Bouzrati-Zerrelli, M.; Villotte, S.; Morlet-Savary, F.; Dietlin, C.; Dumur, F.; Gigmes, D.; Fouassier,

J.P.; Lalevée, J. Polym. Chem. 2016, 7, 5873-5879.



26

Didier Gigmes completed his PhD in organic chemistry in 1998 under the

supervision of Prof. Paul Tordo at the University Paul Cézanne in Marseille

(France). Then he moved to Elf Atochem North America in Pennsylvania (King

of Prussia, PA, USA) to work as a post-doc in the field of controlled radical

polymerization using cobalt derivatives. In 2001, he was recruited as researcher

at CNRS to develop the nitroxide-mediated polymerization (NMP) technique. In

2008, he defended his Habilitation at the University of Provence (Marseille,

France) and in October 2010, he was appointed Research Director at the CNRS

working at Aix-Marseille University (Marseille, France). Currently, with his research group his main

concerns are focused on the development and use of new methodologies for the synthesis of advanced

polymer materials. He is also involved in the development of original methodologies for Nitroxide Mediated

Photopolymerization and the synthesis of versatile photo-initiators. DG is (co)author of 270 peer review

articles in international journals, 15 patents, 10 book chapters and editor of one book on NMP. In 2013, he

was awarded by the Société Chimique de France as « Junior Distinguinshed Member ».



27

Organic and Polymer Free-radical Synthesis using NHC–Boranes

E. Lacôte;a D. P. Curran;b J. Lalevéec; M. Lansalotd and E. Bourgeat-Lami,d

aCNRS, Université Claude Bernard Lyon 1, Villeurbanne, France bUniversity of Pittsburgh (PA), USA

cENSCMu, Université de Haute-Alsace, Mulhouse, France dCNRS, CPE Lyon, Villeurbanne, France

Complexation of boron with N-Heterocyclic carbenes stabilizes boryl radicals and makes them

planar -type radicals. This has important consequences for the reactivity of NHC-borane

complexes. The radical stabilization ensures that they can be introduced in organic free-radical

synthesis and the donation makes the NHC-boryl radicals nucleophilic.

In the talk we will show that NHC-boranes are exquisite reagents for organic reactions and

photopolymerization in organic and disperse media.

• S.-H. Ueng, M. Makhlouf Brahmi, É. Derat, L. Fensterbank, E. Lacôte, M. Malacria, D. P. Curran, J. Am. Chem.

Soc. 2008, 130, 10082-10083, DOI: 10.1021/ja804150k.

• S. Telitel, A.-L. Vallet, S. Schweizer, B. Delpech, N. Blanchard, F. Morlet-Savary, B. Graff, D. P. Curran, M. Robert,

E. Lacôte, J. Lalevée, J. Am. Chem. Soc. 2013, 135, 16938-16947, DOI: 10.1021/ja4066267

• S. Telitel, A.‐L. Vallet, D. M. Flanigan, B. Graff, F. Morlet‐Savary, T. Rovis, J. Lalevée, E. Lacôte, Chem. Eur. J.

2015, 21, 13772-13777, DOI: 10.1002/chem.201500499.



28

Emmanuel Lacôte

EDUCATION AND EMPLOYMENT

2015-present : University of Lyon, Univ. Claude Bernard Lyon 1, (department for hydrazines and polynitrogen energetic compounds), Villeurbanne ; Chair. 2013 : promoted directeur de recherche 1st class, CNRS. 2012 : University of Lyon, CPE Lyon, (department for chemistry, catalysis, polymers and processes), Villeurbanne. 2011 : appointed group leader, Inst. de chimie des subst. naturelles (CNRS), Gif s/ Yvette.

2008 : promoted directeur de recherche 2nd class, CNRS. 2004 : promoted chargé de recherche 1st class, CNRS. 2004 : Habilitation, Université Pierre et Marie Curie, defended September 27. 2000 : appointed chargé de recherche 2nd class, CNRS, U. Pierre et Marie Curie, Paris. 1999-2000 : Postdoctoral fellow, Stanford University, USA (Paul A. Wender). Total Synthesis of

Bryostatin 1 Analogs. 1999 : Ph. D. (joint degree), Université Pierre et Marie Curie / Université de Fribourg (Switzerland),

Advisors: Max Malacria, Philippe Renaud. Applications of Lewis acids in radical chemistry. Defended June 29, 1999.

1991-1995 : undergraduate studies, École Normale Supérieure, Paris

AWARDS

2016 : Bessel Award for research, Alexander v. Humboldt Foundation (Germany) 2012 : JSPS fellow (Chuo University, Tokyo, Japan) 2010 : Scholar in residence, Center of Excellence of the School of Sciences, Tokyo (Japan) 2010 : Excellence in research award, CNRS (PES, first call, renewed 2015). 2009 : Actelion Chair (ENSC Mulhouse) 2003 : Young investigator travel award, 38th Conference on Stereochemistry, Bürgenstock, Suisse 1999 : Lavoisier postdoctoral fellowship (French governement, declined), Cancer research fund award.

INVITED POSITIONS

• 2016: Queen's University, Kingston (ON, Canada) • 2014: Osaka Prefecture University (Japan) • 2012: Westfälische Wilhelms-Universität Münster (Germany) • 2010: University of Tokyo (Japan) • 2010: ENSCMu (France)

5 REPRESENTATIVE PUBLICATIONS

1) "Grafting of Secondary Diol-Amides onto [P2W15V3O62]9– Generates Hybrid Heteropoly Acids" Lachkar, D.; Vilona, D.; Dumont, E.; Lelli, M.; Lacôte, E. Angew. Chem. Int. Ed. 2016, 55, 5961-5965; DOI: 10.1002/anie.201510954. 2) "Polyboramines: Polymers featuring Lewis Pairs in their backbone for Hydrogen Release" Ledoux, A.; Larini, P.; Boisson, C.; Monteil, V.; Raynaud, J.; Lacôte, E. Angew. Chem. Int. Ed. 2015, 54, 15744-15749; DOI: 10.1002/anie.201508395. VIP paper (top 5% Angewandte accepted manuscripts). 3) "Formation of NHC-Boryl Radicals through Electrochemical and Photochemical Cleavage of the B–S bond in N-Heterocyclic Carbene-Boryl Sulfides" Telitel, S.; Vallet, A.-L.; Schweizer, S.; Delpech, B.; Blanchard, N.; Morlet-Savary, F.; Graff, B.; Curran, D. P.; Robert, M.; Lacôte, E.; Lalevée, J. J. Am. Chem. Soc. 2013, 135, 16938-16947; DOI: 10.1021/ja4066267.



29

4) "NHC-Boranes Accelerate Type I Radical Photopolymerizations and overcome Oxygen Inhibition" Lalevée, J.; Telitel, S.; Tehfe, M.-A.; Fouassier, J. P.; Curran, D. P.; Lacôte, E. Angew. Chem. Int. Ed. 2012, 51, 5958-5961. 5) "Complexes of Borane and N-Heterocyclic Carbenes (NHC Boranes): A New Class of Radical Hydrogen Atom Donor" Ueng, S.-H.; Makhlouf Brahmi, M.; Derat, É.; Fensterbank, L.; Lacôte, E.; Malacria, M.; Curran, D. P. J. Am. Chem. Soc. 2008, 130, 10082-10083.



30

Molecular Catalysis of the Photochemical Reduction of CO2 into CO

and beyond: on the Road to Solar Fuels

J. Bonin,* H. Rao and M. Robert

Université Paris Diderot, Sorbonne Paris Cite, Laboratoire d’Electrochimie Moléculaire

UMR 7591 CNRS, 15 rue Jean-Antoine de Baïf, 75205, Paris Cedex 13

*[email protected]

Facing the current environmental and energy issues, the activation of small molecules such as

water, oxygen and carbon dioxide represents a main research challenge.1 In particular, the

generation of solar fuels, namely hydrogen, carbon monoxide, methane or methanol, using

catalysts made of abundant and non-toxic materials and with a minimum energy input is a long

term strategic objective.

To efficiently convert electrons into chemical energy stored in molecular bonds, either by

electrochemical or photochemical ways, processes require a selective and robust catalysis, which

necessitates its intimate understanding at the molecular scale.

In this presentation, I will present both fundamental and applied studies developed at LEM on

the use of molecular homogeneous catalysts based on fourth-period transition metals (Fe, Co, Ni),

and in particular iron porphyrins,2 to catalyze the photochemical reduction of CO2 into CO,3-6 and

beyond.7

(1) Tatin, A.; Bonin, J.; Robert, M. ACS Energy Lett. 2016, 1, 1062.

(2) Bonin, J.; Maurin, A.; Robert, M. Coord. Chem. Rev. 2016, DOI: 10.1016/j.ccr.2016.09.005.

(3) Bonin, J.; Chaussemier, M.; Robert, M.; Routier, M. ChemCatChem 2014, 6, 3200.

(4) Bonin, J.; Robert, M.; Routier, M. J. Am. Chem. Soc. 2014, 136, 16768.

(5) Chen, L.; Guo, Z.; Wei, X.-G.; Gallenkamp, C.; Bonin, J.; Anxolabéhère-Mallart, E.; Lau, K.-C.; Lau, T.-C.;

Robert, M. J. Am. Chem. Soc. 2015, 137, 10918.

(6) Rao, H.; Bonin, J.; Robert, M. Submitted.

(7) Bonin, J.; Schmidt, L. C.; Rao, H.; Robert, M. Submitted.



31

Dr. Julien BONIN Associate Professor of Chemistry

Université Paris Diderot

Laboratoire d'Electrochimie Moléculaire – UMR 7591

15 Rue Jean-Antoine de Baïf

75205 Paris Cedex 13, France

Tel: (33) 1 57 27 87 93

Fax: (33) 1 57 27 87 88

http://www.lemp7.cnrs.fr/

Academic background

2016 / Habilitation à Diriger des Recherches.

June 2012 / Invited scientist, Instituto de Investigaciones en Fisico-química, Universidad Nacional de

Córdoba, Argentina.

December 2011 / Invited scientist, Ångström Laboratory, Uppsala University, Sweden.

Mai-June 2010 / Invited scientist, Department of Chemistry, Massachusetts Institute of Technology,

USA.

Since Sept. 2006 / Associate Professor of Chemistry, LEM, Université Paris Diderot.

2005-2006 / Postdoctoral Research Associate, Radiation Laboratory, of Notre Dame, USA.

2002-2005 / PhD in Molecular Physical Chemistry, Laboratoire de Chimie Physique, Université Paris

Sud 11.

Bibliographic records

26 publications

Research themes

Fundamental approaches of photochemical processes

Proton-coupled electron transfers

Photoinduced electron transfers and bond-breaking

Small molecule activation such as CO2 and protons reduction

Recent publications

1) Rao, H., Bonin, J. & Robert, M. “Non-sensitized Selective Photochemical Reduction of CO2 to CO under

Visible Light with an Iron Molecular Catalyst”, Chem. Commun. 53, 2830-3, 2017.

2) Bonin, J., Maurin, A. & Robert, M., “Molecular Catalysis of the Electrochemical and Photochemical

Reduction of CO2 with Fe and Co Metal Based Complexes. Recent Advances”, Coord. Chem. Rev. 334,

184-98, 2017.

3) Tatin, A., Bonin, J. & Robert, M., “A Case for Electrofuels”, ACS Energy Lett. 1, 1062-4, 2016.

4) Rao, H., Yu, W.-Q., Zheng, H.-Q., Bonin, J., Fan, Y.-T., Hou, H.-W., “Highly Efficient Photocatalytic

Hydrogen Evolution from Nickel Quinolinethiolate Complexes under Visible Light Irradiation”, J. Power

Sources 324, 253-60, 2016.

5) Chen, L., Guo, Z., Wei, X.-G., Gallenkamp, C., Bonin, J., Anxolabehere-Mallart, E., Lau, K.-C., Lau, T.-

C. and Robert, M., “Molecular Catalysis of the Electrochemical and Photochemical Reduction of CO2 with

Earth-Abundant Metal Complexes. Selective Production of CO vs HCOOH by Switching of the Metal

Center”, J. Am. Chem. Soc. 137, 10918-21, 2015.

http://www.lemp7.cnrs.fr/



32

Surface functionalization by model complexes of copper enzymes: the “self-

induced electroclick” approach

N. Le Poula,*

aLaboratoire CEMCA, UMR CNRS 6521, Université de Bretagne Occidentale, Brest, France

*[email protected]

The immobilization of biomimetic redox devices onto solid supports is of particular importance for

the development of efficient sensors and catalysts. It also raises the fundamental question of

coupled electron transfer to reactivity at a metal center. An appealing strategy to address this issue

is to graft a metal center in a well pre-organized and controlled way, such as in self-assembled

monolayers (SAMs). In this context, we have developed a procedure based on the self-induced

electrochemical immobilization of Cu complexes onto pre-modified gold electrodes through a

Cu(I)-catalyzed azide-alkyne Huisgen 1,3-dipolar cycloaddition (“electroclick” reaction).1 Several

molecular and supramolecular biomimetic complexes have been successfully grafted according to

this approach.2-3 Two types of applications have been tested: catalytic reduction of nitrite ions4 and

selective detection of alkylamines5 (Figure) in an aqueous medium.

References

1. Gomila, A.; Le Poul, N.; Cosquer, N.; Kerbaol, J. M.; Noel, J. M.; Reddy, M. T.; Jabin, I.; Reinaud, O.;

Conan, F.; Le Mest, Y., Dalton Trans. 2010, 39 (48), 11516-11518.

2. Orain, C.; Le Poul, P.; Le Mest, Y.; Le Poul, N., J. Electroanal. Chem. 2013, 710, 48-58.

3. Orain, C.; Le Poul, N.; Gomila, A.; Kerbaol, J. M.; Cosquer, N.; Reinaud, O.; Conan, F.; Le Mest, Y., Chem.

Eur J. 2012, 18 (2), 594-602.

4. Orain, C.; Porras-Gutiérrez, A. G.; Evoung Evoung, F.; Charles, C.; Cosquer, N.; Gomila, A.; Conan, F.; Le

Mest, Y.; Le Poul, N., Electrochem. Commun. 2013, 34, 204-207.

5. De Leener, G.; Evoung-Evoung, F.; Lascaux, A.; Mertens, J.; Porras-Gutierrez, A. G.; Le Poul, N.; Lagrost,

C.; Over, D.; Leroux, Y. R.; Reniers, F.; Hapiot, P.; Le Mest, Y.; Jabin, I.; Reinaud, O.,. J. Am. Chem. Soc. 2016, 138

(39), 12841-12853.



33

Nicolas LE POUL (born 1975)

CNRS Researcher (CR1) since 2006, Laboratory CEMCA UMR 6521 CNRS, University of Brest [email protected]; Web page (UBO)

EDUCATION

Master degree (1998), University of Rennes (FR)

Ph.D thesis (2001), University of Exeter (UK)

EXPERIENCES

Ph.D Thesis in Physical Chemistry (2001)“Charge transfer at the HTSC/liquid electrolyte interface” (University of Exeter (UK), Dr. S.J. Green)

Post-doctoral assistant (2002). “Ions sensors based on cathode phosphate materials”(University of Amiens (FR), UMR CNRS 6007, Pr J.-M. Tarascon)

Post-doctoral assistant (2004). “Electrochemical studies of synthetic models of copper enzymes” (University of Brest (FR), UMR CNRS 6521, Dr. Y. Le Mest)

Research engineer (2005). “Post-mortem studies of Li-ion batteries” (BATSCAP-BOLLORE (FR))

RESEARCH AREA

Electrochemistry of inorganic complexes and organic species ; Spectroelectrochemistry; Cryo-spectroelectrochemistry, Surface functionalization; Electrocatalysis.

SCIENTIFIC ACTIVITY

40 publications in international journals with peer view; Yearly participation to international meetings (oral communication).

SELECTED PUBLICATIONS

• "Immobilization of monolayers incorporating Cu funnel complexes onto gold electrodes. Application to the selective electrochemical recognition of primary alkylamines in water", G. De Leener, F. Evoung−Evoung, A. Lascaux, J. Mertens, A. G. Porras−Gutiérrez, N. Le Poul, C. Lagrost, D. Over, Y. R. Leroux, F. Reniers, P. Hapiot, Y. Le Mest, I. Jabin, O. Reinaud, J. Am. Chem. Soc. 2016, 138, 12841−12853.

• "Room−temperature characterization of a mixed−valent µ−hydroxodicopper(II,III)", J. A. Isaac, F. Gennarini, I. Lopez, A. Thibon−Pourret, R. David, G. Gellon, B. Gennaro, C. Philouze, F. Meyer, S. Demeshko, Y. Le Mest, M. Reglier, H. Jamet, N. Le Poul, C. Belle, Inorg. Chem. 2016, 55, 8263−8266.

• "Supramolecular modeling of mono-copper enzyme active sites with calix[6]arene-based funnel complexes", N. Le Poul, Y. Le Mest, I. Jabin, O. Reinaud, Acc. Chem. Res. 2015, 48, 2097-2106.

• "Electrochemically and chemically induced redox processes in molecular machines", N. Le Poul, B. Colasson , ChemElectrochem 2015, 2, 475-496.


https://www.univ-brest.fr/menu/recherche-innovation/pages-chercheurs/LE-POUL-Nicolas/Research-Topics.cid109240

http://pubs.acs.org/doi/abs/10.1021/jacs.6b05317

http://pubs.acs.org/doi/abs/10.1021/jacs.6b05317

http://pubs.acs.org/doi/abs/10.1021/acs.inorgchem.6b01504?journalCode=inocaj

http://pubs.acs.org/doi/abs/10.1021/acs.inorgchem.6b01504?journalCode=inocaj

http://pubs.acs.org/doi/abs/10.1021/acs.accounts.5b00152

http://onlinelibrary.wiley.com/doi/10.1002/celc.201402399/abstract



34

• "Electrocatalytic reduction of nitrite ions by a copper complex attached as SAMs on gold by “self-induced electroclick”: Enhancement of the catalytic rate by surface coverage decrease", C. Orain, A. G. Porras-Gutiérrez, F. Evoung Evoung, C. Charles, N. Cosquer, A. Gomila, F. Conan, Y. Le Mest, N. Le Poul, Electrochem. Commun. 2013, 34, 204-207.

http://www.sciencedirect.com/science/article/pii/S1388248113002464



35

Electron-triggered metamorphism in viologen-based

(supra)molecular materials

C. Kahlfussa, E. Saint-Amanb, E. Dumonta and C. Buchera *

aUniv Lyon, Ens de Lyon, CNRS UMR 5182, Université Claude Bernard Lyon 1, Laboratoire de Chimie, F69342,

Lyon, France. bUniversité Grenoble-Alpes, CNRS, Département de Chimie Moléculaire (UMR 5250), F38400, Grenoble, France.

*[email protected]

The ability to control the structure and organization of molecular materials has emerged in the past

decade as a major scientific objective that is mainly motivated by exciting foreseeable applications

in nanoscience. Enormous technologic interests are for instance at stake in being able to devise

molecular objects that could respond to external stimuli by changes in structure and function. These

particular properties can lead to applications in various domains as (i) in molecular electronics, (ii)

in analytic science, with switchable hosts allowing the controlled binding/release of pollutants or

drugs, (iii) in materials science with the development of adaptive supramolecular polymers.

In this lecture, the syntheses and detailed physico-chemical properties of a series of switchable

molecular architectures whose movements can be triggered by electrochemically driven self-

assembly of organic radicals will be presented.1-8 Particular emphasis will be given to electron-

responsive tweezer-like molecules allowing to control the organization within self-assembled

coordination oligomers/polymers. The dynamic properties of these redox-responsive molecular

architectures and molecular materials will mainly be discussed on the basis of electrochemical,

spectroelectrochemical and ESR experiments supported by quantum chemical calculations.

References

(1) Kahlfuss, C.; Saint-Aman, E.; Bucher, C. “Redox-controlled intramolecular motions triggered by -dimerization

and pimerization “ In Organic Redox Systems: Synthesis, Properties, and Applications; Nishinaga, T., Ed.; John Wiley

and sons, 2016.

(2) Iordache, A.; Oltean, M.; Milet, A.; Thomas, F.; Baptiste, B.; Saint-Aman, E.; Bucher, C. J. Am. Chem. Soc. 2012,

134, 2653.

(3) Iordache, A.; Kanappan, R.; Métay, E.; Duclos, M.-C.; Pellet-Rostaing, S.; Lemaire, M.; Milet, A.; Saint-Aman,

E.; Bucher, C. Org. Biomol. Chem. 2013, 11, 4383.

(4) Kahlfuss, C.; Métay, E.; Duclos, M.-C.; Lemaire, M.; Milet, A.; Saint-Aman, E.; Bucher, C. Chem. Eur. J. 2014,

21, 2090; ibid C. R. Chimie 2014, 17, 505.

(5) Kahlfuss, C.; Milet, A.; Wytko, J. ; Weiss, J.; Saint-Aman, E.; Bucher, C. Org. Lett., 2015, 17 , 4058.

(6) Iordache, A.; Retegan, M.; Thomas, F.; Royal, G.; Saint-Aman, E.; Bucher, C. Chem. Eur. J. 2012, 18, 7648.

(8) Kahlfuss, C.; Denis-Quanquin, S.; Calin, N.; Dumont, E.; Garavelli, M.; Royal, G.; Cobo, S.; Saint-Aman, E.;

Bucher, C. J. Am. Chem. Soc. 2016, 138, 15234.

-ne

+ne

n



36

Dr. Christophe Bucher, 45 years old, obtained a Ph.D. in Physical chemistry from the University of Burgundy at Dijon in 1999 (supervisor: Dr. Jean Michel Barbe). His thesis work involved investigations on the catalytic properties of iron and cobalt cyclam complexes. He was then Postdoctoral Fellow with Professor Jonathan Sessler at the University of Texas at Austin from Nov.1999 to Sept. 2001 working on pyrrole-based macrocycles and cryptands for applications in anion sensing. He started his academic career in 2001 as a CNRS researcher at the University Joseph Fourier-Grenoble in the Laboratory of Organic Electrosynthesis and Redox Photochemistry which became in 2005 the Department of Molecular Chemistry. In 2008 he obtained a HDR diploma delivered by the University of Grenoble. He joined the Ecole Normale Supérieure in Lyon in 2012 where he currently develops his own research activity as a senior CNRS researcher (http://www.ens-lyon.fr/CHIMIE/). He has a fully pluridisciplinary background with expertise ranging from organic synthesis, coordination chemistry and supramolecular chemistry to advanced physical chemistry including molecular/analytical electrochemistry and surface modification. His current fields of interest cover different aspects of supramolecular chemistry, including the design, synthesis and applications of electron-switchable molecular and supramolecular materials with particular emphasis on molecular hosts featuring e-switchable recognition properties and on e-responsive self-assembled supramolecular materials. Since 2004, he has been involved in teaching electrochemistry at ENS-Lyon at the undergraduate and postgraduate levels. He is also involved since 2012 as an expert in molecular electronics for the “Observatoire des Micro et Nanotechnologies (OMNT). Since 2014, he is member of the scientific board of the institute of chemistry in Lyon (ICL) and member of the local board of the French Chemical Society (SCF, Section Rhône-Alpes).

FIELDS OF INTEREST & EXPERTISE

Supramolecular Chemistry & Electrochemistry – Switchable Molecular and Supramolecular Materials – Molecular Machinery – Host-Guest Chemistry – Redox Activation and Sensing . PUBLICATION METRICS/AWARDS

C. Bucher is author or co-author of two book chapters, one patent and of more than 80 articles in peer reviewed international journals. ORCID ID : orcid.org/0000-0003-1803-6733 He has received in 2011 the Young researcher award from the French division of the International Society of Electrochemistry.

CHRISTOPHE BUCHER, PhD Research Director at the National Council for Scientific Research. Department of Chemistry “Supramolecular and Biorganic Chemistry” Group Ecole Normale Supérieure de Lyon [email protected] SCF membership N°: 26545 Tel : +(0033) 472 728 864 ; Fax : +(0033) 472 728 860

http://www.ens-lyon.fr/CHIMIE/

http://www.omnt.fr/index.php/en/

http://www.iclyon.fr/

http://www.societechimiquedefrance.fr/Section-regionale.html




37

Photo-induced redox catalysis for hydrogen production with molecular

compounds

M.-N. Collomb;a* R. Gueret;a C. E. Castillo;a T. Stoll;a J. Chauvin,a F. Odobel,b M. Sliwa,c P.

Lainé,d and J. Fortagea

a Université Grenoble Alpes, CNRS, DCM, UMR 5250, F-38000 Grenoble, France bUniversité Nantes, Univ LUNAM, CEISAM, CNRS,UMR 6230, F-44322 Nantes 3, France

cUniversité Lille 1, CNRS, LASIR, UMR 8516, 59655 Villeneuve d’Asq, France dUniversité Paris Diderot, Sorbonne Paris Cité, ITODYS, UMR CNRS, 15 rue J-A de Baïf, 75013 Paris, France

* [email protected]

Solar driven water-splitting into hydrogen and oxygen, also referred as artificial photosynthesis,

has emerged as a very attractive sustainable approach to produce the fuel H2. Molecular approaches

to generate H2 photochemically typically involve the association of three-components, a light-

harvesting antenna (photosensitizer), a H2-evolving catalyst, and a sacrificial electron donor in

homogeneous solution.1 If a large number of such photocatalytic systems have been reported, very

few of them are able to operate in pure aqueous solution, without co-organic solvent, because of

the lower stability/solubility of molecular compounds in water. However, this is an important

requirement for their further applications in photoelectrochemical water-splitting devices. This talk

will present our efficient systems for the visible-light-driven H2 production in water using rhodium2

and cobalt3 complexes as catalysts and [Ru(bpy)3]2+ as photosensitizer in the presence of ascorbate

as sacrificial electron donor. The advantages of

coupling catalyst and photosensitizer by a covalent

bond will be also presented as well as our promising

results towards the development of systems only

based on earth abundant elements by using a new

water soluble organic dye which represents a very

attractive alternative to [Ru(bpy)3]2+.

Acknowledgments: The authors wish to thank for financial supports the LABEX ARCANE (ANR-11-LABX-0003-

01) for the project H2Photocat and the French National Research Agency for the project HeteroCop (ANR-09-BLAN-

0183-01). This work was also supported by COST CM1202 program (PERSPECT H2O). 1 (a) Stoll, T.; Castillo, C. E.; Kayanuma, M.; Sandroni, M.; Daniel, C.; Odobel, F.; Fortage, J.; Collomb, M.-N., Coord. Chem. Rev., 2015, 304–

305, 20-37. (b) Queyriaux, N.; Kaeffer, N.; Morozan, A.; Chavarot-Kerlidou, M.; Artero V., J. Photochem. Photobiol. C: Photochem. Rev., 2015,

25, 90-105. 2 (a) Stoll, T.; Gennari, M.; Serrano, I.; Fortage, J.; Chauvin, J.; Odobel, F.; Rebarz, M.; Poizat, O.; Sliwa, M.; Deronzier A.; Collomb M.-N., Chem. Eur. J., 2013, 19, 782-792. (b) Stoll, T.; Gennari, M.; Fortage, J.; Castillo, C. E.; Rebarz, M.; Sliwa, M.; Poizat, O.; Odobel, F.;

Deronzier A.; Collomb, M.-N., Angew. Chem., Int. Ed. Engl., 2014, 53, 1654-1658. 3 (a) Varma, S.; Castillo, C. E.; Stoll, T.; Fortage, J.; Blackman, A. G.; Molton, F.; Deronzier A.; Collomb, M.-N. PhysChemChemPhys, 2013, 15, 17544-17552. (b) Gimbert-Surinach, C.; Albero, J.; Stoll, T.; Fortage, J.; Collomb, A. Deronzier, E. Palomares and A. Llobet, J. Am. Chem. Soc.,

2014, 136, 7655-7661. (c) R. Gueret, C. E. Castillo, M.-N.; Rebarz, M.; Thomas, F.; Hargrove, A.-A.; Pécaut, J.; Sliwa, M.; Fortage J.; Collomb

M.-N., J. Photochem. Photobiol., B, 2015, 152, Part A, 82-94.




38

Marie-Noëlle COLLOMB

Marie-Noëlle Collomb, 50 ys. old, is Research Director 2nd class at the CNRS. She is the leader of the group

«Artificial photosynthesis and energy carriers» in the Chimie Inorganique Rédox laboratory (CIRE) at the

Département of Chimie Moléculaire (DCM), Université Grenoble Alpes. She received her Ph. D. from the

Université Joseph Fourier (UJF) of Grenoble in 1993 under the supervision of Alain Deronzier, in the field

of electrocatalytic carbon dioxide reduction with ruthenium carbonyl complexes. After a year working in

the group of Prof. Marc Fontecave on alkanes oxidation catalysis as lecturer at UJF (1993-94), she joined

the CNRS in 1994 as research scientist at UJF. In 1998-99, as a CNRS research associate (NATO

fellowship), she joined the groups of Profs R. H. Crabtree and G. W. Brudvig at Yale University (New

Haven, USA) to develop bioinspired manganese complexes for water oxidation. She was appointed CNRS

Research Director in 2007. Her background ranges from coordination chemistry, electrochemistry and

photo-induced redox catalysis. Her current research interest deals with the development of electrocatalytic

and photocatalytic systems based on transition metal complexes and recently on (oxide) metallic

nanoparticles for artificial photosynthesis applications (H2 production by water reduction and water

oxidation) in homogeneous and in heterogeneous phase (surface modified electrodes, semi-conductor based

photocathodes and photoanodes).

She has supervised 10 PhD thesis, 10 post-doctoral and more than 30 undergraduate and graduate fellows.

She is the author of 101 publications (h-index: 32, (ISI WEB of Knowledge)), two patents, 1 encyclopedia

chapter, and had more than 30 invitations in national and international conferences

(conferences/keynotes/lectures) and in Universities. She is and has been involved as coordinator and partner

in several national and international programs (ANRs (JCJC, blanche), Arcane Labex, CNRS-CONICYT and

ECOS Sud-CONICYT (Chili), Hubert Curien (New-zealand)…). She is also involved as a partner in a COST

ACTION CM1202 « PERSPECT-H2O: Supramolecular photocatalytic water-splitting” and member of the

GDR solar fuels. She has fruitful national and international collaborations (Germany (MPI for Chemical

Energy Conversion, Mulheïm, F.Neese, S. DeBeer, D. Pantazis), Spain (ICIQ Tarragona, A. Llobet, Univ.

of Girona, M. Romero), New-Zealand (Univ. of Auckland, A. G. Blackman), Chili (Univ. of Conception,

B. Luis RIVAS)). She also assumes different responsibilities, e.g. member of the Scientific Council of the

French ANR program "CES06 - Chemistry" (2014), member of the Scientific Council of the French LABEX

program ARCANE (since 2012), member of the Council of the Institute of Molecular Chemistry of

Grenoble (2012-2016) and of the DCM (since 2016), expert for research agencies.



39

Engineering of photocatalytic reactions in microreactors

Timothy Noël*

*Eindhoven University of Technology, Micro Flow Chemistry & Process Technology, Eindhoven, The Netherlands.

[email protected]

Photoredox catalysis is emerging as a new and powerful tool in synthetic organic chemistry to

facilitate photochemical reactions by means of visible light.[1] Notable examples involve the use of

ruthenium(II)polypyridine complexes which upon irradiation produce a photoexcited state. This

photoexcited state gives rise to a single electron transfer process (SET) with organic substrates

which can undergo subsequently a synthetic transformation. Whereas a myriad of different

reactions have recently succumbed to this mode of catalysis, it is important to note that several

challenges still remain with respect to high catalyst loadings, extended reaction times, scalability,

and generality of the catalyst system.

In this oral communication, we will report on the acceleration of gas-liquid photocatalytic reactions

in continuous photomicroreactors.[2] We will go into detail on both engineering and

chemical/catalytic aspects of continuous-flow photochemistry. Relevant examples from our group

will be detailed on during the presentation.[3] Also, we will report on the development of a solar

photomicroreactor, which allows the efficient harvesting of solar energy for photocatalytic

transformations.[4]

[1] For some general reviews on photoredox catalysis: (a) D. M. Schultz and T. P. Yoon, Science, 2014, 343, 1239176.

(b) N. A. Romero and D. A. Nicewicz, Chem. Rev., 2016, 116, 10075-10166. (c) C. K. Prier, D. A. Rankic and D. W.

C. MacMillan, Chem. Rev., 2013, 113, 5322-5363.

[2] For reviews on continuous-flow photochemical processes: (a) D. Cambie, C. Bottecchia, N. J. W. Straathof, V.

Hessel, T. Noël, Chem. Rev. 2016, 116, 10276-10341. (b) Y. Su, N. J. W. Straathof, V. Hessel, T. Noël, Chem. Eur.

J. 2014, 20, 10562-10589.

[3] For selected work on photoredox catalysis from our group: (a) N. J. W. Straathof, S. E. Cramer, V. Hessel, T. Noël,

Angew. Chem. Int. Ed. 2016, 55, 15549-15553. (b) Y. Deng, X.-J. Wei, H. Wang, Y. Sun, T. Noël, X. Wang, Angew.

Chem. Int. Ed. 2017, 55, 832-836. (c) C. Bottecchia, N. Erdmann, P. M. A. Tijssen, L.-G. Milroy, L. Brunsveld, V.

Hessel, T. Noël, ChemSusChem 2016, 9, 1781-1785. (d) N. J. W. Straathof, B. J. P. Tegelbeckers, V. Hessel, X.

Wang, T. Noël, Chem. Sci. 2014, 5, 4768-4773. (e) N. J. W. Straathof, H. P. L. Gemoets, X. Wang, J. C. Schouten,

V. Hessel, T. Noël, ChemSusChem 2014, 7, 1612-1617. (f) X. Wang, G. D. Cuny, T. Noël, Angew. Chem. Int. Ed.

2013, 52, 7860-7864.

[4] D. Cambie, F. Zhao, V. Hessel, M. G. Debije, T. Noël, Angew. Chem. Int. Ed. 2017, 56, 1050-1054



40

Dr. Timothy Noël

Name Timothy Noël

Nationality Belgian

Address Laboratory of Micro Flow Chemistry & Process

Technology, Eindhoven University of Technology, STO

1.37, PO Box 513, 5600 MB Eindhoven, The Netherlands.

E-mail [email protected]

Website www.NoelResearchGroup.com

Professional experience

2012-present Tenured Assistant Professor (Dept. of Chemical Engineering, TU Eindhoven)

• my research group is focused on the combination of reaction engineering,

process technology, organic synthetic chemistry and material science.

2010-2011 Post-doctoral researcher (Massachusetts Institute of Technology, Cambridge,

USA)

• Host: Prof. Dr. Stephen L. Buchwald (Dept. of Chemistry) and collaboration

with Prof. Dr. Klavs F. Jensen (Dept. of Chemical Engineering).

Education

2000-2004 M.Sc. Industrial Chemical Engineer (KaHo Sint Lieven, Ghent, Belgium)

2005-2009 Ph.D. in Organometallic Chemistry (Ghent University, Ghent, Belgium)

• Supervisor: Prof. Dr. Johan van der Eycken

Current Projects

2016 FET Open, NOW, co-applicant (Prof. Hessel Coordinator).

Catalyst Cascade Reactions in ‘One-Flow’ within a Compartmentalized,

Green-Solvent ‘Digital Synthesis Machinery’ – End-to-End Green Process

Design for Pharmaceuticals

3900

k€

2015 VIDI award from Dutch Science Foundation, NWO, personal grant.

Sensitized photoredox catalysis in continuous-flow microreactors

800 k€

2015 Marie Curie Innovative Training Network, coordinator of the project.

Accelerating photoredox catalysis in continuous-flow systems

2,289

k€

2013 ECHO grant from Dutch Science Foundation, NWO.

Breaking the unbreakable: C-H carbonylation in micro flow and vision to

process.

260 k€

Scientific Publications (all are as independent and leading researcher)

101 publications, 14 book chapters, 2 edited books and 1 patent application (To date)

Selected publications

1. A leaf-inspired luminescent solar concentrator for energy efficient continuous-flow

photochemistry. Cambie, D.; Zhao, F.; Hessel, V.; Debije, M.G.; Noël, T. Angew. Chem. Int.

Ed. 2017, 56, 1050-1054 (selected as VIP paper)



41

2. Disulfide-Catalyzed Visible-Light Oxidative Cleavage of C=C Bonds and Evidence of an

Olefin-Disulfide Charge-Transfer Complex. Deng, Y.; Wei, X.-J.; Wang, H.; Sun, Y.; Noël,

T.; Wang, X. Angew. Chem. Int. Ed. 2017, 56, 832-836. (selected as Hot paper)

3. Practical Photocatalytic Trifluoromethylation and Hydrotrifluoromethylation of Styrenes in

Batch and Flow. Straathof, N. J. W.; Cramer, S. E.; Hessel, V.; Noël, T. Angew. Chem. Int.

Ed. 2016, 55, 15549-15553.

4. Mild and selective base-free C–H arylation of heteroarenes: Experiment and computation.

Gemoets, H. P. L.; Kalvet, I.; Nyuchev, A. V.; Erdmann, N.; Hessel, V.; Schoenebeck, F.;

Noël, T. Chem. Sci., 2017, 8, 1046-1055.

5. Applications of continuous-flow photochemistry in organic synthesis, material science and

water treatment. Cambié, D.; Bottecchia, C.; Straathof, N. J. W.; Hessel, V.; Noël, T., Chem.

Rev., 2016, 116, 10276-10341.

Selected Awards

2016 Thieme Chemistry Journal Award.

2015 VIDI Award (Netherlands Organization for Scientific Research, NWO).

2012 Finalist European Young Chemist Award, EuCheMS Conference.

2011 Incentive Award for Young Researchers (Comité de Gestion du Bulletin des Sociétés

Chimiques Belges).



42

Visible light photoredox catalysis with radical anions

I. Ghosh, L. Marzo, R. Shaik, A. Das and B. König*

Faculty of Chemistry and Pharmacy, University of Regensburg, Regensburg, Germany

*[email protected]

Visible light photocatalysis has made a huge impact on recent developments in chemical synthesis.

We have explored over the last two years the use of radical anions as photoactive intermediates in

SRN 1 type reactions. An initial photoinduced electron transfer produces a radical anion, which is

colored and stable. This is excited again to a transient doublet state that is strongly reducing.

Transfer of the excess electron to a substrate, e.g. an aryl halide, initiates the aromatic substitution

reaction. Our initial system based on perylenediimide1 suffered from low solubility of the

photocatalyst and was improved by using the well-established organic dye rhodamine 6G.2

The reaction principle was established for C-C cross coupling reactions,3 the synthesis of annulated

heteroarenes4 and the synthesis of phosphonates.5

Recently, we were able to improve the performance of the reaction further by introducing a

sensitization-induced electron transfer instead of direct excitation of the redox active photo-

catalysts. This new principle generates highly reactive synthesis intermediates with unprecedented

ease from green and blue light.

References

1) I. Ghosh, T. Ghosh, J. I. Bardagi, B. König, Science 2014, 346, 725.

2) I. Ghosh, B. König, Angew. Chem. Int. Ed. 2016, 55, 7676.

3) a) L. Marzo, I. Ghosh, F. Esteban, B. König, ACS Catal. 2016, 6, 6780. B) I. Ghosh, L. Marzo, A. Das, R.

Shaikh, B. König, Acc. Chem. Res. 2016, 49, 1566.

4) A. Das, I. Ghosh, B. König, Chem. Commun. 2016, 52, 8695.

5) R. S. Shaikh, S. J. S. Düsel, B. König, ACS Catal. 2016, 6, 8410.



43

Burkhard König Institut für Organische Chemie Einhausen 38b Universität Regensburg D-93138 Lappersdorf Universitätsstr. 31 Germany D-93040 Regensburg, Germany phone: +49-941-8703153 phone: +49-941-943-4576/5 mobile: +49-15201678001 fax: +49-941-943-1717 e-mail: [email protected]

Curriculum Vitae

Personal data Date of Birth 23/6/1963 Nationality German martial status married, one child Education University education in Chemistry 6/96 venia legendi, Habilitation (organic chemistry), Technical University

of Braunschweig, Germany 9/91 Ph.D. (Dr. rer. nat) (summa cum laude), University of Hamburg,

Germany 9/88 M.S. (Hauptdiplom) (magna cum laude, 1.0), University of Hamburg,

Germany 11/85 B.S. (Vordiplom) (magna cum laude, 1.3), University of Hamburg,

Germany Experience 10/99 - present Full professor at the Department of Chemisty, University of

Regensburg, Germany. Research areas: Physical-organic chemistry; supramolecular chemistry, photocatalysis, catalytic conversion of renewable resources.

6/93 – 9/99 Research group leader at the Department of Chemistry, Technical University of Braunschweig, Germany.

1/92 - 5/93 Postdoctoral fellow with Prof. Dr. B. M. Trost at Stanford University, U.S.A.

10/91 - 1/92 Visiting research fellow with Prof. Dr. M. A. Bennett at the Research School of Chemistry, Australian National University, Canberra, Australia

3/88 - 9/91 Graduate research with Prof. Dr. A. de Meijere at the University of Hamburg

Awards and activities



44

• Editorial board member of “Chemistry – A European Journal” and “European Journal of Organic Chemistry (Chair) (since 2014)

• UN-Decade Award on Sustainability 2011/2012

• Dean of the faculty of chemistry since 10/2011

• Literature award of the Fonds of the German Chemical Industry 2007

• Chairman of the Liebig Vereinigung (National organic devision; 2008 – 2012)

• Member of the excecutive board of the German Chemical Society (2004 - 2007)

• Chairman of the „Arbeitsgemeinschaft Deutscher Universitätsprofessoren Chemie (ADUC)

• (2005-2007)

• Member of the International Advisory Board of the Institute for Organic Chemistry and Biochemistry of the Czech Academy of Sciences, Prag (since 2004)

• Member of the International Advisory Board of the “European Journal of Organic Chemistry” (since 2004)

• Invitation fellowship award of the `Japan Society for the Promotion of Science´ (1996)

• Award of the Dr. Otto Röhm Gedächnisstiftung (1995)

• Fellowship of the Deutsche Forschungsgemeinschaft (Habilitationsstipendium)

• Fellowship of the Fonds der Chemischen Industrie (Liebig-Stipendium)

• Postdoctoral fellow of the Alexander von Humboldt foundation (Feodor-Lynen fellow)

• Graduate fellow of the Studienstiftung des Deutschen Volkes

Publication record Scientific papers and reviews: 314 / H-index 45 books, book reviews, science related articles: 60

Regensburg 11/2016 For additional information, please visit: http://www-oc.chemie.uni-regensburg.de/koenig/index.html

Ten self selected papers

1. Eosin Y Catalyzed Visible Light Oxidative C-C and C-P bond Formation (Times Cited: 238)

D. P. Hari, B. Koenig* Org. Lett. 2011, 13, 3852 – 3855. DOI: 10.1021/ol201376v

The paper disclosed the first example of using the organic dye eosin Y as visible light photocatalyst;

the compound is now widely used by researchers to replace precious Ru(bipy)3Cl2 in synthesis.

2. Metal free, Visible Light Mediated Direct C-H Arylation of Heteroarenes with Aryl Diazonium salts

(Times Cited: 200)

D. P. Hari, P. Schroll, B. König* J. Am. Chem. Soc. 2012, 134, 2958 – 2961. DOI: 10.1021/ja212099r

The Meerwein arylation reaction is known since more than 100 years, but the original protocol using

copper salts gives only moderate yields. This has limited the use of the reaction in synthesis. We

describe here for the first time the activation of diazonium salts by visible light photoredox catalysis

providing a much cleaner reaction and good to excellent product yields. The “Photo Meerwein”

reaction has since then been widely applied in organic synthesis.

http://www-oc.chemie.uni-regensburg.de/koenig/index.html



45

3. The Photocatalyzed Meerwein Arylation: Classic Reaction of Aryl Diazonium Salts in a New Light

(Times cited: 204)

D. P. Hari, B. König* Angew. Chem. Int. Ed. 2013, 52, 4734 – 4743. DOI: 10.1002/anie.201210276

We have summarized the rapid expanding synthetic applications of our „Photo Meerwein“ arylation

reaction in this review.

4. Visible Light Photocatalytic Synthesis of Benzothiophenes (Times Cited: 85)

D. P. Hari, T. Hering, B. König* Org. Lett. 2012, 14, 5334 – 5337. DOI: 10.1021/ol302517n

Application of the „Photo Meerwein“ reaction in the synthesis of important heterocycles.

5. Visible light Promoted Stereoselective Alkylation by Combining Heterogeneous Photocatalysis with

Organocatalysis (Times Cited: 85)

M. Cherevatskaya, M. Neumann, S. Füldner, C. Harlander, S. Kümmel, S. Dankesreiter, A. Pfitzner,

K. Zeitler, B. König* Angew. Chem. Int. Ed. 2012, 51, 4062 – 4066. DOI: 10.1002/anie.201108721

This is the first report combining stereoselective organocatalysis with heterogeneous semiconductor

photocatalysis replacing homogeneous photocatalysts, like Ru or Ir complexes by robust and available

semiconductors.

6. Reduction of aryl halides by consecutive visible light-induced electron transfer processes (Times Cited:

33)

I. Ghosh, T. Ghosh, J. I. Bardagi, B. König* Science 2014, 346, 725-728.

This is the first report on consecutive photoinduced electron transfer in visible light photocatalysis.

7. Molecular Imprinting of Luminescent Vesicles (Times Cited: 21)

S. Banerjee, B. König* J. Am. Chem. Soc. 2013, 135, 2967 – 2970. DOI: 10.1021/ja4001568

First report of molecular imprinting on the surface of a fluid vesicle giving luminescent nanosensors.

8. Regulation of Human Carbonic Anhydrase I (hCAI) Activity by Using a Photochromic Inhibitor (Times

Cited: 50)

D. Vomasta, C. Högner, N. R. Branda,* B. König* Angew. Chem. Int. Ed. 2008, 47, 7644 - 7647.

DOI: 10.1002/anie.200802242

Photochromic enzyme inhibitor based on a dithienylethene chromophore allows the reversible light

controlled inhibition of an enzyme.

9. Potent and selective inhibitors of breast cancer resistance protein (ABCG2) derived from the p-

glycoprotein (ABCB1) modulator tariquidar (Times Cited: 62)

M. Kühnle, M. Egger, C. Müller, A. Mahringer, G. Bernhardt, G. Fricker, B. König,* A. Buschauer*

J. Med. Chem. 2009, 52, 1190 – 1197. DOI: 10.1021/jm8013822

The compound with currently highest potency and selectivity for ABCG2 inhibition is reported.

10. Conversion of carbohydrates into 5-hydroxymethylfurfural in highly concentrated low melting mixtures

(Times Cited: 91)

F. Ilgen, D. Ott, D. Kralisch, C. Reil, A. Palmberger, B. König* Green Chem. 2009, 11, 1948 – 1954.

DOI: 10.1039/b917548m First report of the efficient and solvent-free conversion of carbohydrates into

HMF using a low melting mixture.



46

New photoredox-induced cascade reactions

Malte Brasholza,*

aUniversity of Hamburg, Department of Chemistry – Institute of Organic Chemistry, Hamburg, Germany

[email protected]

Photoredox-mediated one-electron reduction of organic halides is a mild and efficient method to

generate the corresponding carbon-centered radicals. While the reduction of activated acyl halides

can readily be accomplished using common ruthenium(II) polypyridyl photocatalysts, unactivated

alkyl, alkenyl and aryl halides require more strongly reducing conditions, and in particular

iridium(III) polyheteroaryl complexes possess suitable redox potentials to bring about these more

challenging reductive transformations.1

Photoinduced free radical additions have been utilized extensively in the synthesis of

functionalized heterocycles, however, mostly giving aromatic products. We developed

dearomative radical additions onto indoles, and an iridium(III)-catalyzed reductive radical (4+2)-

cyclization between N-iodoethylindoles and alkenes led to valuable tricyclic benzindolizidine

products.2 Further extension of our methodology enabled a new stereoselective synthesis of

functionalized hexahydrocarbazoles, based on an unprecedented dearomative radical (4+2)-

cyclization/1,4-addition cascade between 3-(2-iodoethyl)indoles and acceptor-substituted alkenes.

The photoredox-induced cascade reaction simultaneously generated three C-C and one C-H bonds,

along with three contiguous stereogenic centers.3

Mechanistic aspects of these dearomative radical cyclizations of indole derivatives will be

discussed, as well as synthetic applications of the heterocyclic products, which are highly valuable

intermediates for the synthesis of novel antibiotics as well as unnatural ring homologs of polycyclic

indoline alkaloids.

References

[1] Reviews: (a) C. K. Prier, D. A. Rankic, D. W. C. Mac Millan, Chem. Rev. 2013, 113, 5322-5363.

(b) D. Ravelli, S. Protti, M. Fagnoni, Chem. Rev. 2016, 116, 9850-9913.

[2] S. Mühmel, D. Alpers, F. Hoffmann, M. Brasholz, Chem. Eur. J. 2015, 21, 12308-12312.

dearomative radical (4+2)-cyclization (4+2)-cyclization / 1,4-addition cascade



47

[3] D. Alpers, M. Gallhof, J. Witt, F. Hoffmann, M. Brasholz, Angew. Chem. 2017, 129, 1423-1427; Angew. Chem.

Int. Ed. 2017, 56, 1402-1406.

Malte Brasholz studied Chemistry at Freie Universität Berlin and obtained his PhD from the

same institution in 2007, under the guidance of Prof. Hans-Ulrich Reissig. A short-term stay in

the laboratory of Prof. Hisashi Yamamoto at the University of Chicago in 2008 was followed by

one year of postdoctoral research in the group of Prof. Steven V. Ley at the University of

Cambridge. A second year of postdoctoral studies led Malte to Australia, where he worked at

CSIRO Molecular and Health Technologies in association with Prof. Andrew B. Holmes at the

University of Melbourne. In 2010, he was appointed Research Scientist at CSIRO Materials

Science and Engineering. From April 2012, Malte established an independent research group at

the Institute of Chemistry at the University of Hamburg.

Academic CV

.

2012 Assistant Professor of Organic Chemistry, University of Hamburg

2010 Research Scientist, CSIRO Materials Science and Engineering, Melbourne

2009 Postdoctoral fellow, CSIRO Molecular and Health Technologies

and group of Prof. Andrew B. Holmes, University of Melbourne

2008 Postdoctoral fellow, group of Prof. Steven V. Ley, University of Cambridge

2007 Short-term scholar, group of Prof. Hisashi Yamamoto, University of Chicago

2007 PhD in Chemistry, group of Prof. Hans-Ulrich Reissig, Freie Universität Berlin

2004 Diplom degree in Chemistry, group of Prof. Hans-Ulrich Reissig, Freie Universität Berlin

Awards and Fellowships:

.

2016 GIAN lectureship, Government of India

2015 Donation by Dr. Otto Röhm Gedächtnisstiftung

2014 Thieme Journal Award

2009 Postdoctoral fellowship, CSIRO Office of the CEO Awards Scheme

2008 Postdoctoral fellowship, Deutsche Forschungsgemeinschaft (DFG)

2005 PhD fellowship, Fonds der Chemischen Industrie (FCI)



48

Photoinduced Electron Transfer in Base-promoted Homolytic Aromatic

Substitution and Related Systems. Is t-butoxide anion a key ingredient?

M. E. Budén;a J. F. Guastavino,a J. I. Bardagí, a Marcelo Puiatti a and R. A. Rossia*

a Instituto de Investigaciones en Físicoquímica de Córdoba, INFIQC, Córdoba, Argentina

*[email protected]

In the recent years, there is a booming of research in transition metal-free couplings of ArX to

arenes to form biaryls (eq 1). These reactions are triggered by alkali metal tert-butoxides in the

presence of various additives via Base-promoted Homolytic Aromatic Substitution (BHAS).1,2 In

2008, the original report presented by Itami showed that KOtBu promoted the arylation of pyrazine

and other electron‐poor arenes from ArI or ArBr, under elevated temperatures or MW irradiation.3

Later, different research groups have reported the construction of biaryls and stilbene derivatives

from unactivated aromatic compounds by direct C-H activation of benzene or styrene using

NaOtBu or KOtBu in the presence of a range of organic additives as ligands.2 As a consequence,

the role of these organic additives in radical initiation attracted much research interest and different

mechanisms have been proposed.4

Previously we reported on photoredox reactions for synthesis of biaryls (BHAS) and styrenes

(Mizoroki−Heck-type) as a new alternative to induce these transformations at room temperature

(eqs 1 and 2).5 Now, we propose a new alternative to induce these photoreactions, that involves

dimsyl anion as a key ingredient. However, C-H functionalization of alkenes is produce without

any solvent. Computational studies were performed to help to understand the initiation steps of

these processes.

1. Studer, A.; Curran, D. P. Angew. Chemie Int. Ed. 2011, 50, 5018–5022.

2. a) Sun, C.; Shi, Z. Chem. Rev. 2014, 114, 9219–9280. b) Hussain, I.; Singh, T. Adv. Synth. Catal. 2014, 356, 1661–

1696. c) Mehta, V. P.; Punji, B. RSC Adv. 2013, 3, 11957 and references cited herein.

3. Yanagisawa, S.; Ueda, K.; Taniguchi, T.; Itami, K. Org. Lett. 2008, 10, 4673–4676.

4. a) Zhou, S.; Anderson, G. M.; Mondal, B.; Doni, E.; Ironmonger, V.; Kranz, M.; Tuttle, T.; Murphy, J. A. Chem.

Sci. 2014, 5, 476–482. b) Zhou, S.; Doni, E.; Anderson, G. M.; Kane, R. G.; MacDougall, S. W.; Ironmonger, V. M.;

Tuttle, T.; Murphy, J. A. J. Am. Chem. Soc. 2014, 136, 17818–17826. c) Patil, M. J. Org. Chem. 2016, 81, 632–639.

5. a) Budén, M. E.; Guastavino, J. F.; Rossi, R. A. Org. Lett. 2013, 15, 1174–1177. b) Guastavino, J. F.; Budén, M.

E.; Rossi, R. A. J. Org. Chem. 2014, 79, 9104–9111.

mailto:*[email protected]



49

María Eugenia Budén

Address Ernesto La Padula 865. (CP 5000), Cordoba, Argentine

Telephone (+54) 0351 460 2736

Nationality Argentine

Date of birth

e-mail

13th of August 1981

[email protected]

CURRENT RESEARCH POSITION

From April 2013

Assistant researcher at CONICET. Title: Photoinduced Direct C-H-Arylation via Base-Promoted

Homolytic Aromatic Substitution

FELLOWSHIP AWARDS

From April 2010 to March 2012

Postdoctoral Research Fellowship from the National Research Council of Argentina.

Title: Synthesis of Biaryls and Heterocycles by Metal-Catalyzed Organic Reactions and SRN1.

Research Advisor: Dr. Roberto A. Rossi and Sandra E. Martin

From April 2005 to March 2010

Doctoral Research Fellowship from the National Research Council of Argentina. Thesis Title: New

Tandem Reactions by SRN1 Mechanisms. Research Advisor: Dr. Roberto A. Rossi.

RESEARCH INTERESTS

Organic synthesis and photochemistry – Radical chemistry – Redox processes in organic syntheses –

Heterocyclic chemistry-.

SCIENTIFIC PUBLICATIONS

13 papers, 5 chapter of books and 22 oral and poster presentations.

STAYS IN INTERNATIONALLY RECOGNIZED CENTRES

From April 2011 to October 2011

Laboratori de Química Farmacèutica (Unitat Associada al CSIC), Facultat de Farmàcia, Universitat

de Barcelona, Barcelona, Spain.

Topic: Tetrasubstituted alkenes by metathesis of 1,1-disubstituted alkenes: potential application for

the synthesis of belt compounds

Research Advisor: Dr. Pelayo Camps




50

KOtBu promoted intermolecular cross-coupling through electron transfer

A. Tlili,a,* J. Bergèsb and M. Tailleferb,*

aICBMS - SURCOOF (UMR CNRS 5246 - Lyon), Villeurbanne, France bENSCM - UMR 5253 - Institut Charles Gerhardt, Montpellier, France (Times New Roman, italicized in 10 pt.)

*[email protected]

The talk will mainly focus on our recent ongoing research program based on transition metal free

cross-coupling reactions. Indeed, we recently developed a Matsuda-Heck coupling reaction

allowing the formation of stilbenes derivatives using arenediazonium salts and styrene derivatives

as coupling partners. Theses reactions proceed under transition metal and irradiation-free

conditions.1

1.J. Bergès, A. Tlili, M. Taillefer, manuscript in preparation

R

N2+BF4

-

+R

KOtBuR'

R'



51

Anis TLILI [email protected] ICBMS-SURCOOF + 33 4 72 44 85 28 Université Claude Bernard - Lyon 1

43 Bd du 11 novembre 1918

Bat. Raulin (4ème étage)

69622 Villeurbanne Cedex – France

Date of birth: February 25, 1983, Married

CNRS Research Fellow

Experience

10/2014- CNRS Research Fellow

To date ICBMS - SURCOOF (UMR CNRS 5246 - Lyon), Université Claude Bernard - Lyon 1.

09/2013- Chercheur postdoctoral, CEA - Commissariat à l'énergie atomique -Saclay, France.

08/2014 Synthesis of new phosphine based frustrated Lewis pair for the reduction of CO2.

In collaboration with the group of: Dr. A. Marinetti

01/2012- Chercheur postdoctoral, Leibniz-Institut für Katalyse, Allemagne, Prof. M. Beller.

08/2013 Transition metals catalyzed reactions under carbon monoxide.

2011 Internship (2 months), ENS Paris, France, Supervised by Dr. A. Jutand.

Electrochemical studies on Cu-catalyzed C-N and C-O Bond formating reactions

2008-2011 Thèse en chimie, ENSC Montpellier, France, Dr. M. Taillefer.

Cu -catalyzed C-C, C-N and C-O Bond formating reactions.

2007-2008 Master internship (6 mois), Université de Bourgogne, Dijon, France, Prof. S.

Jugé.

New P-Chirogenic diphosphine complexes.

PUBLICATIONS AND PATENTS

33 publications & patents

2 book chapters

Awards

First Price IDEAS COMPETITION “CATALYSIS 2020“, Leibniz-Institut für Katalyse

Awarded Leibniz grant for Post-doctoral researcher (01/2012-08/2013), Leibniz-Institut für

Katalyse

Solvias AG lecture 2016



52

“The Palme d’Or goes to …”. A search for the best functional for dealing with

anionic organic species

M. Puiatti;a,* J. L. Borioni;b D. M. A. Vera b and A. B. Pierinia,

aINFIQC- Instituto de Investigaciones en Físicoquímica de Córdoba, Córdoba, Argentina b Dpto. Química, Fac. Cs. Exactas y Naturales, Universidad Nacional de Mar del Plata, Mar del Plata, Argentina

* [email protected]

During the last few decades, density functional theory (DFT) has become the method of choice

in quantum chemical studies. Indeed, many experimental investigations routinely include such

calculations, using a popular code, a standard basis, and a standard functional approximation.1 It is

well known that DFT has provided approximations that work quite well for some problems and fail

for others.2 Hence, a proper recommendation should be to search for the DFT functional that works

better within the problem to be studied. In the present study we addressed the overall performance

of 23 different DFT functionals and ab initio methods for studying anionic organic species.

In order to evaluate its scope and limitations, electron affinities (EA) and reduction potentials

(𝐸𝑅𝑒𝑑0 ) were computed. A set of 60 molecules was employed for the calculation of EAs, in the range

of 0 to -3.4 eV. Besides, 62 compounds were selected for the computation of the 𝐸𝑅𝑒𝑑0 , with

potentials, measured in acetonitrile, from -2.71 V to 0.06 V (vs. standard hydrogen electrode, SHE).

For compounds with negative EAs, hybrid GGA gave better results than pure and meta GGA double

hybrid functionals and ab initio methods yield poorly with MADs higher than 0.5 eV.

The calculations of 𝐸𝑅𝑒𝑑0 are strongly dependent on the quality of the solvation energies of the

charged species. This was evidenced in the correlation of calculated absolute 𝐸𝑅𝑒𝑑0 vs. experimental

𝐸𝑅𝑒𝑑0 . However, there is a significant improvement after the use of a proper redox partner. The best

results were obtained with hybrid GGA functionals, B3PW91 and PBE0. TPSSh and M06 were

the better meta GGA. Pure GGA functionals gave good results, with low dispersion, but high

MADs, that could improve by choosing a proper reference.

mailto:*%[email protected]



53

The ideal scenario should give a podium with some functionals that outperform the others.

However, there is a suitable DFT functional for each problem instead of a universal one that could

solve almost all the situations within different conditions.

References:

1- Burke, K., J Chem Phys, 2012, 136, 150901.

2- Medvedev, M. G.; Bushmarinov, I. S.; Sun, J.; Perdew, J. P.; Lyssenko, K. A. Science, 2017, 355, 49-52.



54

MARCELO PUIATTI

Nationality: Argentine

Date of Birth: 10th of February 1977

Address: Arq. Ernesto La Padula 865. Ba: Parque Vélez Sarsfield. Córdoba. Argentina.

Telephone: +54-351-156742579

Email: [email protected]

[email protected]

CURRENT POSITION

From 2004

From 2009

Assistant Profesor. Facultad de Ciencias Químicas. Universidad Nacional de Córdoba.

Researcher. INFIQC. CONICET. “Application of Molecular Modeling to the Study of Organic and Bio-organic Systems”. Former Director: Prof. Dra. Adriana B. Pierini

RESEARCH INTEREST

Electron Transfer Reactions; Radical Anions; DFT; Photochemistry; AChE Inhibitors; Molecular Modeling

SCIENTIFIC PUBLICATIONS

11 Scientific Articles, 25 Presentations to Workshops and Scientific Meetings, 3 Invited Conferences.

MOST RELEVANT ARTICLES

“In search of the best DFT functional for dealing with organic anionic species”. José L. Borioni, Marcelo Puiatti, D. Mariano A. Vera and Adriana B. Pierini. Phys. Chem. Chem. Phys. Accepted. doi: 10.1039/C6CP06163J. “In search for an optimal methodology to calculate the valence electron affinities of temporary anions.” Puiatti, M.; Vera, D.M.A; Pierini, A. B.. Phys. Chem. Chem. Phys., 2009, 11, 9013 - 9024. “Species with negative electron affinity and standard DFT methods. Finding the valence anions” Marcelo Puiatti, D. Mariano A. Vera, Adriana B. Pierini. Phys. Chem. Chem. Phys., 2008, 10,1374-1379.

FORMATION

2006. PhD. Doctor en Ciencias Químicas. “Study of Electron Transfer Oxidation Reactions”. Advisor: Dra. Alicia B. PEÑÉÑORY. Fac. de Cs. Químicas. Universidad Nacional de Córdoba.



55

2006-2009 Post-doctoral Position. “Computational Chemistry Applied to Study of Intermediate Species of Electron Transfer Reactions”. Director: Dra. Adriana B. Pierini. Fac. Ciencias Químicas. Universidad Nacional de Córdoba. Post-doctoral Fellowship CONICET.

2011-2012 Post-doctoral Position. Life Sciencies Department BSC Barcelona. “Electronic and Atomic Protein Modeling”. Director: Dr. Víctor Guallar. 01/02/2011 hasta 28/02/2012. MAE Fellowship Spain.



56

Characterization of single electron transfer steps in water oxidation through

DFT calculations

Feliu Maseras

a Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science of Technology, Av. Països Catalans 16,

43007 Tarragona, Catalonia, Spain (Times New Roman, italicized in 10 pt.) bDepartament de Química, Universitat Autònoma de Barcelona, 08193 Bellaterra, Catalonia, Spain

* [email protected]

Computational homogeneous catalysis has been traditionally dominated by two-electron transfer

processes.1 The increasing interest in the catalytic processes involving first row transtion metals

has lead to the identification of a number of processes where single electron transfer processes play

a critical role.2-6 In this presentation we will discuss some of our recent contributions in the field,

with a special focus on copper-catalyzed O-O water oxidation3,6 (see Figure). Calculations

demonstrate that single electron transfer processes replace in some cases the two-electron transfer

water nucleophilic attack mechanism, the main operating mode for second- and third-row transition

metals.

References (Times New Roman, 10 pt.), denoted by superscript numbers in the text, it should be listed at the end of

the text using ACS format. 1. Sameera, W. M. C.; Maseras, F. WIREs Comp. Mol. Sci. 2012, 2, 375-385. 2. Jover, J.; Spuhler, P.; Zhao, L. G.; McArdle, C. Catal. Sci. Tech. 2014, 4, 4200- 4209. 3. Garrido-Barros, P.; Funes-Ardoiz, I.; Drouet, S.; Benet-Buchholz, J.; Maseras, F.; Llobet, A. J. Am. Chem. Soc.

2015, 137, 6758-6761. 4. Fernandez-Alvarez, V. M.; Nappi, M.; Melchiorre, P.; Maseras, F. Org. Lett. 2015, 17, 2676-26795. 5. Funes-Ardoiz, I.; Maseras, F. Angew. Chem. Int. Ed. 2016, 55, 2764-2767. 6. Funes-Ardoiz, I.; Garrido-Barros, P.; Llobet, A.; Maseras, F. ACS Catal. 2017, DOI:10.1021/acscatal.6b03253



57

Feliu Maseras

Contact information

[email protected]

Experience

Research group leader in Institute of Chemical Research of Catalonia (ICIQ) since 2004

Assoc Prof in Universitat Autònoma de Barcelona since 1998

Assoc Researcher in Montpellier 1996-98

Post-doctoral researcher in Okazaki 1992-94

Education

PhD in Chemistry, Universitat Autònoma de Barcelona, 1991

Research topics

Research interest focused in the design an application of QM/MM methods to problems of

practical interest and the computational study of the reactivity of molecular systems containing

transition metal atoms.



58

Charge Transfer Processes : Prime Role of Optimized Molecular Orbitals

V. Roberta,*, A. Domingoa, T. Kraha and B. Meyera

aLaboratoire de Chimie Quantique, CNRS Université de Strasbourg, Strasbourg, France

*[email protected]

abstract : The key role played by the molecular orbitals in describing electron transfer processes

is examined in mixed-valence compounds (see Figure, Fe3+/Fe2+ biomimetic non-heme1) and

analogues. It is suggested that the extent of

electronic reorganization induced by

intervalence charge transfer can reach up to

several electron-volts2,3. By means of ab initio

calculations (wave-function type,

CASSCF/CASPT2), it is shown that the

energetic profile shows strong similarities to the

Marcus’s theory. Such observation questions

the standard quantum chemistry approaches

used to describe internal electron transfer

phenomena in molecular science devices.

References: 1. Balasubramanian, R.; Blondin, G.; Canales, J. C.; Costentin, C.; Latour, J.-M.; Robert, M.; Savéant, J.-M. J Am.

Chem. Soc. 2012, 134, 1906. 2. Domingo, A.; Angeli, C.; de Graaf, C.; Robert, V. J. Comp. Chem. 2015, 36, 861. 3. Meyer, B. Domingo, A.; Krah, T.; Robert, V. Dalton. Trans. 2014, 43, 11209.



59

Vincent ROBERT Date of birth: March 17th 1969

E-mail: [email protected] - webpage: http://quantique.u-strasbg.fr/pperso/vincent/

CURRENT POSITION

Full Professor Strasbourg University, Laboratoire de Chimie Quantique

Director of Laboratoire de Chimie Quantique, Strasbourg

Director of Réseau Chimie Théorique Français Grand-Est

Member of LabEx Complex Systems, Strasbourg University

Coordination Leader ANR French Research Project (2007-2010)

Supervisor 1 PhD, 1 PostDoc

SCIENTIFIC BACKGROUND 2010-present Full Professor (section 31), Strasbourg University

1997-2010 Assistant Professeur, Physical Chemistry, Lyon 1 University

2001-2003 Sabbatical CNRS, Laboratoire de Chimie et Physique Quantiques,

Toulouse

SCIENTIFIC ACTIVITIES semi empirical calculations, ab initio, methodology - spectroscopies, magnetic systems,

macroscopic properties, spintronics

Publication (98) 62 ACS, APS Journals and 36 in Eur. Journals

2 reviews, 2 book chapters, 3 cover pages

Invited Professor Nagoya University, Japan, September 2007, 2009, 2012

Tarragona University, Spain, April-May 2008

Conferences 20 invited conferences, 30 invited seminars

5 Reference Publications

1. Mizumo, A.; Shuku, Y.; Suizu, R.; Matsushita, M.; Tsuchiizu, M.; Reta Maneru, D.; Illas,

F.; Robert, V.; Awaga, K. J. Am. Chem. Soc. 2015, 137, 7612

2. Domingo, A.; de Graaf, C.; Angeli, C.; Robert, V. J. Comp. Chem. 2015, 36, 861

3. Krah, T.; Ben Amor, N.; Maynau, D.; Berger, J.A.; Robert, V. J. Mol. Mod. 2014, 20, 2240

4. Vérot, M.; Borshch, S.A.; Robert, V. J. Chem. Phys. 2013, 138, 094105

5. Perraud, O.; Robert, V.; Gornitzka, H.; Martinez, A.; Dutasta, J.P. Angew. Chem. Int. Ed.

2012, 51, 504



60

Exploring the reactivity of the Kagan’s reagent from a theoretical perspective

L. Perrin;a,* X. Zhaob and L. Maronb

aUniversité Lyon 1, CNRS, INSA, CPE, UMR 5246, ICBMS, ITEMM, 43 Bd du 11 novembre 1918, 69622

Villeurbanne cedex, France b LPCNO, Université de Toulouse, INSA, UPS, CNRS, 135 avenue de Rangueil, F-31077 Toulouse, France

*[email protected]

The Kagan’s reagent (SmI2) is one of the most versatile single-electron reducing agent in organic

synthesis. Since its seminal report,1 the scope off application of this reagent has been largely

enriched by adjusting the reaction conditions and especially the proper solvent / co-solvent(s)

combinations.2 Modeling single electron transfer mediated by f-element proved to be inaccessible

until recently.3 This contribution details the modeling strategy developed for the modeling of the

reactivity SmI2 in complex environments and addresses how co-solvents such as HMPA, water and

amine not only modify the reducing power of SmI2 but also strongly affect reaction mechanisms.

More precisely, our pioneering mechanistic investigation addresses the mechanism by which alkyl-

halides and various carbonyl derivatives are selectively reduced by SmI2 depending on the reaction

conditions.4 A particular emphasis will be laid on the role played by bimetallic intermediates and

subsequent Bimetallic Proton Coupled Electron Transfer (BPCET).

FIG. Bimetallic reduction of aliphatic esters by SmI2 in ternary THF/water/amine

Namy, J. L.; Girard, P.; Kagan, H. B. Nouv. J. Chim. 1977, 1, 5; Girard, P.; Namy, J. L.; Kagan, H. B. J. Am. Chem.

Soc. 1980, 102, 2693.

Procter, D. J.; Flowers, R. A., II; Skrydstrup, T. Organic Synthesis Using Samarium Diiodide: A Practical Guide;

RSC Publishing: Cambridge, 2010; Szostak, M.; Procter, D. J. Angew. Chem., Int. Ed. 2011, 50, 7737. Szostak, M.;

Spain, M.; Procter, D. J. Chem. Soc. Rev. 2013, 42, 9155.

Kefalidis, C. E.; Essafi, S.; Perrin, L.; Maron, L. Inorg. Chem. 2014, 53, 3427.

Kefalidis, C. E.; Perrin, L.; Maron, L. Eur. J. Inorg. Chem. 2013, 22-23, 4041 and unpublished results.

Lionel Perrin received his Ph.D. in 2004 from Université Montpellier (Odile Eisenstein and Laurent Maron directors) and joined the CNRS in 2005. Since 2013, he is group leader of Interface Theory Experiment: Mechanism and Modeling (ITEMM) at Université Lyon 1, he focuses on the interplay between experiments and theory for polymerization and multistep organic reactions catalyzed by organometallic species.

Curriculum 2016 « Habilitation à Diriger des Recherches » Université Lyon 12004-2005 CNRS Post-doctoral fellow, CEA-Saclay2001-2004 PhD of Theoretical Physiocal-Chemistry Université Montpellier II

2000-2001 Master of Theoretical Physiocal-Chemistry Université Toulouse III1997-2000 Ingénieur Chimiste Ecole Supérieure de Chimie Organique et Minérale ESCOM

Lab Experiences2013- Chargé de recherche au CNRS (UMR 5246, ICBMS), Univ-Lyon 1

ITEMM Group leader Theoretical/experiment interface, molecular modeling and reaction mechanism exploration. Folding and self-assembly mechanism.

2008-2013 Chargé de recherche au CNRS (UMR 5215, LPCNO), INSA-Toulouse Computational chemistry applied to organometallic and bio-inorganic chemistry

2005-2008 Chargé de recherche au CNRS (URA 2096, PMTE), CEA-Saclay Modeling of the dynamics and reactivities of metalloproteins

2004-2005 Post-doctoral fellow at CEA-Saclay, F. André et M. Delaforge (CNRS valorisation / Servier)Computational investigation of recognition mechanism of P450s

2001-2004 Thèse de doctorat à l’Université Montpellier II, O.Eisenstein et L.Maron (Michelin, CIFRE) Theoretical investigation of the structure and reactivity of organolanthanide complexes

Major CollaboratorsR.A. Andersen UC-Berkeley, USAI. Marek Technion Haifa, IsraëlD.J. Procter University of Manchester, UK S. Maeda Hokkaido University, JaponK. Morokuma FIFC-Kyoto, Japon

C. Boisson CPE-LyonM. Taoufik CPE-LyonC. Taillefumier Université Clermond-FerrandO. Eisenstein Université Montpellier IIManufacture MICHELIN

Recent publicationsDeciphering selectivity in organic reactions: A multifaceted problem. Balcells D, Clot E, Eisenstein O, Nova A, Perrin L: Acc. Chem. Res. 49:1070-1078, 2016Spécial Issue on Computational Catalysis for Organic Synthesis Preparation and Reactivity of Acyclic Chiral Allylzinc Species via a Zn-Brook Rearrangement. Leibeling M, Shurrush KA, Perrin L, Marek I: Angew. Chem. Int. Ed. 55:6057-6061, 2016Weak backbone CH…O=C and side chain tBu…tBu London interactions help promote helix folding of achiral NtBu peptoids. Angelici G, Bhattacharjee N, Roy O, Faure S, Didierjean C, Jolibois F, Perrin L*, Taillefumier: Chem. Commun. 52:4573-4576, 2016New perspectives in organolanthanide chemistry from redox to bond metathesis: Insights from theory. Kefalidis CE, Castro L, Perrin L, Del Rosal I, Maron L: Chem. Soc. Rev. 45:2516-2543, 2016. Ethylene-Butadiene Copolymerization by Neodymocene complexes: a Ligand Structure / Activity / Polymer Microstructure Relationship based on DFT calculations. Nsiri H, Belaid I, Larini P, Thuilliez J, Boisson C, Perrin L*: ACS Catal. 6:1028-1036, 2016.

2017 workshop « electron transfer, radical ions and radical chemistry … · 2017-03-14 · that...

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