Catalytic synthesis and transformations of organophosphorus compounds

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  • MendeleevCommunications

    Focus Article, Mendeleev Commun., 2008, 18, 113120

    113 2008 Mendeleev Communications. All rights reserved.

    Irina P. Beletskaya is a professor and head of the Laboratory of Organoelement Compounds at the Departmentof Chemistry, M. V. Lomonosov Moscow State University, and a full member of the Russian Academy of Sciences.I. P. Beletskaya is the Chief Editor of the Russian Journal of Organic Chemistry. From 1989 to 1991, she wasthe president of the Organic Chemistry Division of the IUPAC. I. P. Beletskaya has been awarded many Russianand international awards: Arbuzov award (2007), RF State award (2004), Demidov award (2003), Lomonosov,Mendeleev, Kapitsa and Nesmeyanov awards. She is a honorary academician of Bashkortostan, as well as honoraryprofessor of Cordoba University, Royal Stockholm University and St. Petersburg Technical University. Her scientificinterests include organic and organoelement synthesis, catalysis with transition metal complexes and organic catalysis.

    Maria M. Kabachnik is a candidate of chemical sciences and assistant professor at the Department of Chemistryof M. V. Lomonosov Moscow State University. M. M. Kabachnik is an author of about 250 publications, including15 inventor certificates and patents. Her scientific interests lie in the chemistry of organophosphorus compounds:development of new methods for the synthesis of compounds of three- and four-coordinate phosphorus andpreparation of new biologically active compounds based on natural phosphorus-containing porphyrins.

    Dedicated to the 100th anniversary of Academician M. I. Kabachnik

    Catalytic synthesis and transformationsof organophosphorus compounds

    Irina P. Beletskaya* and Maria M. KabachnikDepartment of Chemistry, M. V. Lomonosov Moscow State University, 119991 Moscow, Russian Federation. Fax: +7 495 939 3618; e-mail: beletska@org.chem.msu.ru

    DOI: 10.1016/j.mencom.2008.05.001Methods for the catalytic synthesis of organophosphorus compounds with three- and four-coordinate phosphorus and theirtransformations are summarised. Special attention is given to the synthesis of aryl(vinyl)-substituted phosphonates andphosphinates, as well as aminophosphonates, which are of particular interest due to their high biological activity.

    Catalytic synthetic methods that allow the limits of fine organicsynthesis to be expanded considerably play a special role insynthetic organic chemistry. Catalytic methods are currentlyused in synthetic organophosphorus chemistry to obtain variousorganophosphorus compounds, in particular, functionalised phos-phonates and phosphinates, which attract a special attention dueto their biological activity.

    The diversity of organophosphorus compounds is determinedby the position of phosphorus in a periodic system of theelements and by its ability to form one- to six-coordinatephosphorus compounds and bonds with both electropositiveand electronegative elements.

    Organic phosphorus derivatives are successfully used asbiologically active compounds, complexing reagents, ligandsin complexes with transition metals, phosphorus-containingpolymers and reagents in organic syntheses.

    The biological activity of organophosphorus compounds wasnot always used for the good of the people. The most toxicorganophosphorus compounds, such as fluoro- (or cyano)-con-taining phosphonates and thiophosphonates behaving as neuro-paralytic agents, were created as second-generation chemicalweapons (sarin, saman, tabun and VX). These weapons havekilled many human lives; furthermore, destruction of suchweapons (which is mandatory for all nations that have signed

    the Convention) presents a major problem (especially for ourcountry) as it requires significant financial expenses.1

    However, it is owing to the chemical activity of organo-phosphorus compounds that medical agents such as Alafosfalineand Fosmidomicine were obtained from them.2

    The majority of these compounds are the derivatives of-aminophosphonic acids, i.e., the phosphorus analogues of-aminocarboxylic acids.

    The use of organophosphorus compounds in agriculture aspesticides, plant growth regulators, etc., is of considerableimportance.2 Roundup, a popular agent, contains fragmentsof both -aminocarboxylic and -aminophosphonic acids.

    H2NHN P(OH)2

    O

    OAlafosfaline

    OHCN

    P(OH)2O

    OHFosmidomicine

    (HO)2P NH COOHO

    Glyphosate (Roundup)

  • 114

    Focus Article, Mendeleev Commun., 2008, 18, 113120

    The complexing capability of diphosphonates gave anopportunity to create a series of organophosphorus complexons,such as hydroxyethylidenediphosphonic acid, ethylenediamine-tetramethylphosphonic acid and many others, which have beenstudied in detail by M. I. Kabachnik et al. and used in theextractive metallurgy of non-ferrous metals, trace metals andprecious metals.35

    Organic phosphines, phosphites, phosphinites and amido-phosphinites are widely used in homogeneous catalysis asligands in transition-metal complexes.68 The very existence ofthis area, which is of primary importance in todays chemistry,especially in its infancy, was due to the use of phosphinecomplexes of palladium, platinum, rhodium, etc. The use oftransition-metal complexes with chiral phosphine ligands ascatalysts is of particular interest when performing asymmetrichydrogenation, hydroformylation and many other reactions. Thesecatalysts enabled the syntheses of enantiomerically pure com-pounds, including the most significant pharmaceuticals. Many ofchiral phosphine ligands became commercially available, thoughthey are difficult to synthesise.

    Phosphorus-containing polymers are used less commonly.However, they possess valuable properties, such as fire-resistanceand inertness to chemical reagents, which make them interestingfrom a practical point of view.9

    Organophosphorus compounds find extensive use in organicsynthesis. This primarily includes well-known olefination reac-tions: Wittig reaction and PO olefination, that is, the reactionof phosphorus-containing carbanions with carbonyl compounds(the HornerWoodwardEmmons reaction).

    In the majority of reactions, the phosphorus atom acts as anucleophile. These include the classical Arbuzov, MichaelisBecker, Pudovik, KabachnikFields and Abramov reactionsthat allow one to obtain various organophosphorus compounds,as well as the Mitsunobu and Staudinger reactions that provideways to synthesise diverse organic compounds, such as amines,esters, imides and phosphazo compounds.

    There are also reactions where PIII or PV compounds act aselectrophiles. Among them are the interactions of PIII halideswith trialkylphosphites10 or ambident imine anions. In the lattercase, dialkylchlorophosphines attack a carbon atom of theambident system to give functionally substituted phosphines.11The use of PCl3 makes it possible to obtain N-phosphorus(III)-substituted enamines; it has been shown that, initially, PCl3reacts with these anions at a carbon atom, but then, if the tem-perature is increased, the PCl2 group migrates to the nitrogenatom to give phosphorylated enamines (Scheme 1).12

    Reactions of R2PCl, RPCl2 and PCl5 with electron-donatingalkynes containing CspOR or CspNR2 bonds involve electro-philic trans-addition to the triple bond to give the correspondingphosphorus-containing alkenes (Scheme 2).13

    The chemistry of low-coordinate phosphorus derivatives isanother interesting area in the chemistry of organophosphorus

    compounds.1419 For example, two-coordinate phosphorus deriva-tives with a P=N bond react with alkynes to give varioushitherto-unknown compounds, such as phosphirenes, azaphos-phetines and azaphosphabutadienes, depending on the substituents(Scheme 3).20,21

    Catalytic substitution producing a Csp2P bondCatalytic reactions with the formation of a Csp2P bond proved

    to be quite efficient in syntheses of aryl and vinyl derivatives oftetracoordinate phosphorus, which were difficult to access before.It is well known that the Arbuzov reaction involving aryl andvinyl halides occurs at high temperatures in the presence ofnickel complexes as catalysts.2224 The use of trimethylsilyl-phosphites instead of usual trialkylphosphites allowed us todecrease the reaction temperature and to obtain aryl(hetaryl)-phosphonic acids in high yields after treatment of correspondingarylphosphonates with methanol (Scheme 4).25,26

    R2

    R1R3

    NR4Et2NLi

    Et2NH

    R2

    R1R3

    NR4

    Li+

    R2PClhexane 70 C

    R2PNR4

    R3

    R1 R2

    hexane 70 C PCl3

    Cl2PNR4

    R3

    R1 R2

    R1, R2, R3 = Alk, HR, R4 = Alk

    R1N

    R3

    R2

    PCl2

    R4

    room

    temperature

    Scheme 1

    R1 OR2RPCl2 +R(Cl)P

    R1 Cl

    OR2R = AlkR1 = Alk, Me3Si, Me3GeR2 = Alk

    R NR1

    R

    R2P NR1

    Cl

    2 2 P R2R2

    Cl

    NR1R 2A B

    R2PCl2 R2PCl2

    R = R1 = EtR2 = Pri

    A:B = 10:90 (hexane) 53:47 (benzene) 100:0 (CH2Cl2)

    PCl5 + R OR1Cl2P

    R Cl

    OR1

    O

    R1Cl Cl2P

    R

    O

    O

    R = But, Ph, Me3Si, CH2OMeR1 = Alk

    Scheme 2

    2

    P

    Alk2Alk1

    R NAr

    P

    OAlk2Alk1

    R NAr

    R = Ph, But

    P

    NAlk2Alk1

    But NAr

    2

    P NBut Ar

    NAlk2Alk1 2

    +

    RP NAr

    R1 R2+

    P NN Ar

    AlkEt2N

    Ar

    Me3Si

    R2 = But, SiMe3

    CAlk1

    Alk2 P

    OAlk3

    Me3SiHNN(SiMe)2

    Hal

    Alk2O

    P

    R1

    NAr

    Hal = Cl, Br,

    Alk2N

    Hal

    P

    R1

    NAr

    R1 = Alk12

    P

    OAlk2Alk1

    NAr P NHal Ar

    NAlk2Alk1 2

    Alk1Alk2O

    Hal

    Scheme 3

    R2 = OAlk2

  • 115

    Focus Article, Mendeleev Commun., 2008, 18, 113120

    The reaction of trial

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