sp c-h alkylation with olefinsgbdong.cm.utexas.edu/seminar/old/12-03-2014 sp3 c-h... · 1) sp3 c-h...
TRANSCRIPT
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sp3 C-H Alkylation with Olefins
,
Yan Xu
Dec. 3, 2014
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1) sp3 C-H Alkylation via Directed C-H activation
2) Hydroaminoalkylation (still via C-H activation)
3) Hydrohydroxyalkylation (via radical chemistry)
4) Hydrohydroxyalkylation (via transfer hydrogenation chemistry)
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1) sp3 C-H Alkylation via Directed C-H activation
2) Hydroaminoalkylation (still via C-H activation)
3) Hydrohydroxyalkylation (via radical chemistry)
4) Hydrohydroxyalkylation (via transfer hydrogenation chemistry)
Rare-earch-metal-philic DG
Allylic C-H bond alkylation (double bond as DG)
Pyridine type DG
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1) sp3 C-H Alkylation via Directed C-H activation
2) Hydroaminoalkylation (still via C-H activation)
3) Hydrohydroxyalkylation (via radical chemistry)
4) Hydrohydroxyalkylation (via transfer hydrogenation chemistry)
Rare-earch-metal-philic DG
Allylic C-H bond alkylation (double bond as DG)
Pyridine type DG
Yong-Qiang Tu, Angew. Chem. Int. Ed. 2009, 48, 8761
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1) sp3 C-H Alkylation via Directed C-H activation
2) Hydroaminoalkylation (still via C-H activation)
3) Hydrohydroxyalkylation (via radical chemistry)
4) Hydrohydroxyalkylation (via transfer hydrogenation chemistry)
Rare-earch-metal-philic DG
Allylic C-H bond alkylation (double bond as DG)
Pyridine type DG
Michael J. Krische, Science. 2012, 336, 324
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sp3 C-H Alkylation with Olefins
Through C-H activation,
Yan Xu
Dec. 3, 2014
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1) sp3 C-H Alkylation via Directed C-H activation
2) Hydroaminoalkylation (still via C-H activation)
Rare-earch-metal-philic DG
Allylic C-H bond alkylation (double bond as DG)
Pyridine type DG
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Zhaomin Hou, ACIE. 2012, 51, 12828 –12832
Rare-earth metal:
Strong oxophilicity
High activity of rare-earth alkyl species toward olefin
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Zhaomin Hou, ACIE. 2012, 51, 12828 –12832
Rare-earth metal:
Strong oxophilicity
High activity of rare-earth alkyl species toward olefin
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Olefin: must be terminal
Ethylene: oligomer
Zhaomin Hou, ACIE. 2012, 51, 12828 –12832
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Olefin: must be terminal
Ethylene: oligomer
Zhaomin Hou, ACIE. 2012, 51, 12828 –12832
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Olefin: must be terminal
Ethylene: oligomer
Zhaomin Hou, ACIE. 2012, 51, 12828 –12832
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Zhaomin Hou, ACIE. 2013, 52, 4418
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Zhaomin Hou, ACIE. 2013, 52, 4418
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Zhaomin Hou, ACIE. 2013, 52, 4418
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Zhaomin Hou, ACIE. 2013, 52, 4418
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KIE = 3.7
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KIE = 3.7
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KIE = 3.7
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T. Don Tilley J. Am. Chem. Soc., 2003, 125, 7971
non-reactive substrates:cis/trans-2-butene, 1-hexene,1-butene, 2-methylpropene, norbornylene, and 2-butyne
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Zhi-Xiang Yu, JACS. 2010, 132, 4542
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Zhi-Xiang Yu, JACS. 2010, 132, 4542
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Zhi-Xiang Yu, JACS. 2010, 132, 4542
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Zhi-Xiang Yu, ACIE. 2011, 50, 2144
Zhi-Xiang Yu, Organometallics, 2012, 31, 5185
Diene coordinationdisfavored the double-bond isomerization
Bis-allylic Rh complex facilitate the reductive elimination
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Zhi-Xiang Yu, ACIE. 2011, 50, 2144
Zhi-Xiang Yu, Organometallics, 2012, 31, 5185
Diene coordinationdisfavored the double-bond isomerization
Bis-allylic Rh complex facilitate the reductive elimination
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Zhi-Xiang Yu, ACIE. 2011, 50, 2144
Zhi-Xiang Yu, Organometallics, 2012, 31, 5185
Diene coordinationdisfavored the double-bond isomerization
Bis-allylic Rh complex facilitate the reductive elimination
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Chul-Ho Jun Chem. Commun., 1998, 1405
95%
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Chul-Ho Jun Chem. Commun., 1998, 1405
95%
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Chul-Ho Jun Chem. Commun., 1998, 1405
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Shinji Murai J. Am. Chem. Soc., 2001, 123, 10935
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Shinji Murai J. Am. Chem. Soc., 2001, 123, 10935
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Shinji Murai J. Am. Chem. Soc., 2001, 123, 10935
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Olefin part substrate scope is similar as Jun’s
Shinji Murai J. Am. Chem. Soc., 2001, 123, 10935
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Shinji Murai J. Am. Chem. Soc., 2001, 123, 10935
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Shinji Murai J. Am. Chem. Soc., 2001, 123, 10935
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1) H/D exchange experiment “ provided good evidence for the reversibility of C-H bonds between substrates and reactants (alkenes),indicating that the cleavage of C-H bonds is not the rate-determining step”
2)
Shinji Murai J. Am. Chem. Soc., 2001, 123, 10935
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Bert U. W. Maes Chem. Eur. J. 2012, 18, 10393
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Bert U. W. Maes Chem. Eur. J. 2012, 18, 10393
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Bert U. W. Maes Chem. Eur. J. 2012, 18, 10393
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Bert U. W. Maes Chem. Eur. J. 2012, 18, 10393
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“ carboxylic acid / alcohol has a significant effect on catalyst initiation ”
Bert U. W. Maes Chem. Eur. J. 2012, 18, 10393
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Bert U. W. Maes Chem. Eur. J. 2012, 18, 10393
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Bert U. W. Maes Adv. Synth. Catal. 2014, 356, 1610
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[Ru] = (PCy3)2(CO)RuHCl
Chae S. Yi Organometallics 2004, 23, 5392
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catalytic active
1)
2) kNH /kND = 1.9
(consistent with a rate-limiting
N-H bond activation step)
1 = (PCy3)2(CO)RuHCl
Chae S. Yi Organometallics 2004, 23, 5392
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Takanori Shibata Org. Lett., 2011, 13, 4692
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For substrate scope:R = Me, EtOlefin = styrene, diene,
ee = 61-90%terminal olefin’s yield is low
Takanori Shibata Org. Lett., 2011, 13, 4692
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For substrate scope:R = Me, EtOlefin = styrene, diene,
ee = 61-90%terminal olefin’s yield is low
Takanori Shibata Org. Lett., 2011, 13, 4692
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Takanori Shibata Tetrahedron 68 (2012) 9009
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Till Opatz Org. Lett., 2014, 16, 4201
Reaction condition:Acrylate, Vinylsilane (DME, 85 ℃)Styrene, vinylboronic ester, 1-hexene (DME, 140 ℃)
42% 64%
better substrate scope
63%
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Till Opatz Org. Lett., 2014, 16, 4201
Reaction condition:Acrylate, Vinylsilane (DME, 85 ℃)Styrene, vinylboronic ester, 1-hexene (DME, 140 ℃)
42% 64%
better substrate scope
63%
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60 %
46 %
Dalibor Sames J. Am. Chem. Soc., 2004, 126, 6556
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60 %
46 %
Dalibor Sames J. Am. Chem. Soc., 2004, 126, 6556
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60 %
46 %
Dalibor Sames J. Am. Chem. Soc., 2004, 126, 6556
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Kinetic competent and chemical competent catalyst
Dalibor Sames J. Am. Chem. Soc., 2004, 126, 6556
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Guangbin Dong, Science 2014, 345, 68
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1) sp3 C-H Alkylation via Directed C-H activation
2) Hydroaminoalkylation (still via C-H activation)
Rare-earch-metal-philic DG
Allylic C-H bond alkylation (double bond as DG)
Pyridine type DG
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1) sp3 C-H Alkylation via Directed C-H activation
2) Hydroaminoalkylation (still via C-H activation)
Rare-earch-metal-philic DG
Allylic C-H bond alkylation (double bond as DG)
Pyridine type DG
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toluene, 200 oC, 150h
Maspero, F. Synthesis 1980, 305.
* Isolated by distillation
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Nugent, W. A Organometallics 1983, 2, 161
yield not given“ The activity of the various metal amides for this reaction roughly parallels their efficacy for H-D exchange”
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Nugent, W. A Organometallics 1983, 2, 161
yield not given“ The activity of the various metal amides for this reaction roughly parallels their efficacy for H-D exchange”
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John Hartwig J. Am. Chem. Soc., 2007, 129, 6690
zirconocene-η2-imine complexes was formed faster from N-alkyl arylamido complexes than from dialkylamido complexes.
Nugent, W. A Organometallics 1983, 2, 161
Organometallics 1994, 13, 190
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John Hartwig J. Am. Chem. Soc., 2007, 129, 6690
Nugent, W. A Organometallics 1983, 2, 161
Organometallics 1994, 13, 190zirconocene-η2-imine complexes was formed faster from N-alkyl arylamido complexes than from dialkylamido complexes.
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Cannot use styrene and 1,2-disubstituted olefin
John Hartwig J. Am. Chem. Soc., 2007, 129, 6690
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John Hartwig J. Am. Chem. Soc., 2008, 130, 14940
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John Hartwig J. Am. Chem. Soc., 2008, 130, 14940
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John Hartwig J. Am. Chem. Soc., 2008, 130, 14940
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John Hartwig J. Am. Chem. Soc., 2008, 130, 14940
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Sven Doye Angew. Chem. Int. Ed. 2009, 48, 1153
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Sven Doye Angew. Chem. Int. Ed. 2009, 48, 1153
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Sven Doye Angew. Chem. Int. Ed. 2009, 48, 1153
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Sven Doye Angew. Chem. Int. Ed. 2009, 48, 1153
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Sven Doye Angew. Chem. Int. Ed. 2009, 48, 1153
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Sven Doye ChemCatChem 2009, 1, 162
[Ti(Bn)4]
Sven Doye Angew. Chem. Int. Ed. 2009, 48, 1153
Slightly enhanced activity First addition to styrene: 30% yield, 1:1 branch:linear
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Sven Doye ChemCatChem 2009, 1, 162
[Ti(Bn)4]
Sven Doye Angew. Chem. Int. Ed. 2009, 48, 1153
Slightly enhanced activity First addition to styrene: 30% yield, 1:1 branch:linear
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Laurel L. Schafer J. Am. Chem. Soc., 2009, 131, 2116
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Laurel L. Schafer J. Am. Chem. Soc., 2009, 131, 2116
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Zr: larger metal center 2-pyridonate ligand: less sterically demanding
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Zr: larger metal center 2-pyridonate ligand: less sterically demanding
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Laurel L. Schafer Angew. Chem. Int. Ed. 2009, 48, 8361
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1
Laurel L. Schafer Angew. Chem. Int. Ed. 2009, 48, 8361
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Laurel L. Schafer Angew. Chem. Int. Ed. 2009, 48, 8361
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60%R = Ph 68%R = Me 43% See: Org. Lett., 2013, 15, 2182
Laurel L. Schafer Angew. Chem. Int. Ed. 2009, 48, 8361
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For further improvement, See: Guofu Zi, Chem. Commun., 2010, 46, 6296Guofu Zi, Dalton. Trans., 2011, 40, 1547
Laurel L. Schafer Angew. Chem. Int. Ed. 2009, 48, 8361
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Only 105 oC: is this catalyst able to solve the styrene problem?
Sven Doye Angew. Chem. Int. Ed. 2010, 49, 2626
Sven Doye Angew. Chem. Int. Ed. 2009, 48, 1153
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Only 105 oC: is this catalyst able to solve the styrene problem?
Sven Doye Angew. Chem. Int. Ed. 2010, 49, 2626
Sven Doye Angew. Chem. Int. Ed. 2009, 48, 1153
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Sven Doye Angew. Chem. Int. Ed. 2010, 49, 2626
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Sven Doye Angew. Chem. Int. Ed. 2010, 49, 2626
Sven Doye Chem. Eur. J. 2013, 19, 3833
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Sven Doye, Angew. Chem. Int. Ed. 2011, 50, 6401
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Sven Doye, Angew. Chem. Int. Ed. 2011, 50, 6401
Zero-order rate dependence on aminoalkene
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Sven Doye, Angew. Chem. Int. Ed. 2011, 50, 6401
Zero-order rate dependence on aminoalkene
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Sven Doye, Angew. Chem. Int. Ed. 2011, 50, 6401
kobs(1-H)/kobs (1-D) = 7.3 at 130oC
with 5 mol% and 10 mol% [Ti(NMe2)4]
Zero-order rate dependence on aminoalkene
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Sven Doye, Angew. Chem. Int. Ed. 2011, 50, 6401
kobs(1-H)/kobs (1-D) = 7.3 at 130oC
with 5 mol% and 10 mol% [Ti(NMe2)4]
Zero-order rate dependence on aminoalkene
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Sven Doye, Angew. Chem. Int. Ed. 2011, 50, 6401
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Kai C. Hultzsch J. Am. Chem. Soc., 2012, 134, 3300
59-98% ee
61-95% yield
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Non-dissociative
Fast
reversible
r.d.s:
Either by amide exchange
Or by alkene insertion
Catalyst activity can be enhanced by a more electron deficient ligand
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Laurel L. Schafer Chem. Eur. J. 2013, 19, 8751
84% 73% 61%130 oC
36%145 oC
Styrene disubstituted terminal alkenes internal unstrained alkenes dialkylamines.
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Laurel L. Schafer Chem. Eur. J. 2013, 19, 8751
84% 73% 61%130 oC
36%145 oC
16%145 oC
85%
Styrene disubstituted terminal alkenes internal unstrained alkenes dialkylamines.
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Laurel L. Schafer Chem. Eur. J. 2013, 19, 8751
84% 73% 61%130 oC
36%145 oC
Styrene disubstituted terminal alkenes internal unstrained alkenes dialkylamines.
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84% 73% 61%130 oC
36%145 oC
Styrene disubstituted terminal alkenes internal unstrained alkenes dialkylamines.
Laurel L. Schafer Chem. Eur. J. 2013, 19, 8751
Laurel L. Schafer Tetrahedron 2013, 69, 5737
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Laurel L. Schafer Angew. Chem. Int. Ed. 2013, 52, 9144
minimum temperature required to achieve at least three turnovers within 20 h
sufficient steric bulk is critical Electron withdrawing ligand is critical
Phosphoramidates increased electronwithdrawing properties tunable steric bulk at both phosphorus and nitrogen
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Laurel L. Schafer Angew. Chem. Int. Ed. 2013, 52, 9144
minimum temperature required to achieve at least three turnovers within 20 h
sufficient steric bulk is critical Electron withdrawing ligand is critical
Phosphoramidates increased electronwithdrawing properties tunable steric bulk at both phosphorus and nitrogen
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Laurel L. Schafer Angew. Chem. Int. Ed. 2013, 52, 9144
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Laurel L. Schafer Angew. Chem. Int. Ed. 2013, 52, 9144
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Laurel L. Schafer Org. Lett., 2013, 15, 6002
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Ta−Cl bond [2.4959(8) Å] is significantly longer than Ta−NMe2(axial) bond [1.970(3) Å] the bonding the of Ta−N amido bond lengths are shorter in 1 than in 2
Improved metal accessibility increased electrophilic nature of the metal center
e-withdrawing and steric less hindered ligand!
Laurel L. Schafer J. Am. Chem. Soc., 2014, 136 (31), pp 10898
Laurel L. Schafer Org. Lett., 2013, 15, 6002
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Laurel L. Schafer J. Am. Chem. Soc., 2014, 136 (31), pp 10898
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Laurel L. Schafer J. Am. Chem. Soc., 2014, 136 (31), pp 10898
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Laurel L. Schafer J. Am. Chem. Soc., 2014, 136 (31), pp 10898
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Another unsolved problem: Styrene selectivity w/ [Ti]
Branched selectivity: has already been achieved by [Ta]
Eur. J. Org. Chem. 2014, 2790
a:b>99:1
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Linear selectivity?
Schafer’s catalyst for intramaleculor HAA reaction
By NMR
Sven Doye Angew. Chem. Int. Ed. 2013, 52, 1806
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Summary
sp3 C-H alkylation has been achieved via many different machanism
Metal: d0 & d8
Logical development of ligand and catalyst is critical
Inspiration of our own work
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Summary
sp3 C-H alkylation has been achieved via many different machanism
Metal: d0 & d8
Logical development of ligand and catalyst is critical
Inspiration of our own work
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“The predominance of multiply deuterated products, especially from the Zrcatalyst, suggests that further metalation of the intermediate metallacycle is fast compared with the reverse reaction.”
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