Enatioselective and Enantiospecific Transiton- Metal ...
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Supervisor: Prof. Huang
Reporter: Sixuan Meng
2015-08-24
Enatioselective and Enantiospecific Transiton-
Metal-Catalyzed Cross-Coupling Reactions of
Organometallic Reagent To Construct C-C bond
Sarash E. Reisman et al. Chem. Rev. ASAP
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Content
• Introduction
• Enantioselective Transition-Metal-Catalyzed Alkyl Cross-
Coupling Reactions
Reactions of secondary Alkylmetallic Reagents
Reactions of secondary Alkyl Electrophiles
• Transition-Metal-Catalyzed Enantiocontrolled Allylic
Substitution
Enantioselective Allylic Substitution Reactions
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Instroduction
• Transition-metal-catalyzed Cross-coupling Reaction
C−C bond forming reactions between an organic electrophile (typically
an organic halide or pseudohalide, which in this review includes alcohols,
amines, and their derivatives) and an organometallic reagent, mediated by
a transition-metal catalyst.
• Enantiospecific Cross-Coupling
chirality exchange reactions in which the stereochemistry of a chiral,
enantioenriched substrate defines the stereochemistry of the product.
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• Enantioselective Cross-Coupling
Reactions in which there
is selective formation of
one enantiomer over the
other as defined by a chiral
metal catalyst.
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Content
• Introduction
• Enantioselective Transition-Metal-Catalyzed Alkyl Cross-
Coupling Reactions
Reactions of secondary Alkylmetallic Reagents
Reactions of secondary Alkyl Electrophiles
• Transition-Metal-Catalyzed Enantiocontrolled Allylic
Substitution
Enantioselective Allylic Substitution Reactions
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Enantioselective Transition-Metal-Catalyzed Alkyl Cross-Coupling
Reactions
• Reactions of secondary Alkylmetallic Reagents
In principle, fast equilibration between the two enantiomers of a sec-
alkylmetallic reagent or between two diastereomers of a chiral transition
metal complex could enable enantioselective cross-coupling through a
dynamic kinetic asymmetric transformation (DYKAT)
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Organomagnesium Reagent
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Kumada, M. et al. Tetrahedron Lett. 1974, 15, 3
Kumada, M. et al. Tetrahedron Lett. 1977, 18, 1389
Brunner, H. et al. J. Organomet. Chem. 1981, 209, C1
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• Proposed catalytic cycle for the enantioselective coupling of
α-methylbenzyl Grignard reagents
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• Coupling of disubstituted alkenes
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• Coupling of α-Silyl Grignard Reagents
Kumada, M. et al.
J. Org. Chem.
1986, 51, 3772
Kumada, M. et al.
Tetrahedron Lett.
1981, 22, 137
Kumada, M. et al.
Tetrahedron Lett.
1983, 24, 807
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Organozinc Reagent (Negishi-type)
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Ito, Y. et al. Chem. Commun. 1989, 495
Reisman, S. E. et al. Tetrahedron 2014, 70, 3259
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• Enantioconvergent alkyl-alkyl coupling
Fu, G. C. et al. J. Am. Chem. Soc. 2013, 135, 10946
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Organoboron Reagents
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• Dual catalysis approach to asymmetric cross-coupling
Molander, G. A. et al. Science 2014, 345, 433
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Reactions of secondary Alkyl electrophiles
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With Organomagnesium Reagent (Kumada-Corriu)
17 Fu, G. C. et al. J. Am. Chem. Soc. 2010, 132, 1264
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With Organozinc Reagent (Negishi)
Fu, G. C. et al. J.
Am. Chem. Soc.
2005, 127, 4594
Fu, G. C. et al. J.
Am. Chem. Soc.
2005, 127, 10482
Alkylzinc
Reagent
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Arylzinc Reagent
Fu, G. C. et al. J. Am. Chem. Soc. 2008, 130, 12645
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20 Fu, G. C. et al. Angew. Chem. Int. Ed., 2009, 48, 154
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Fu, G. C. et al. JACS.
2014, 136, 12161
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With Organoboron Reagent (Suzuki-Miyaura)
22 Fu, G. C. et al. J. Am. Chem. Soc. 2008, 130, 6694
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Examples of directing groups for enatioconvergent Suzuki-Miyaura coupling
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24 Fu, G. C. et al. J. Am. Chem. Soc. 2010, 132, 11027
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25 Fu, G. C. et al. J. Am. Chem. Soc. 2014, 136, 3788
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Transition-Metal-Catalyzed Enantiocontrolled Allylic Substitution
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General principles of allylic substitution with hard nucleophiles
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Enantioselective Allylic Substitution Reactions
Organomagnesium Reagents
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Seminal Example of Cu-Catalyzed Asymmetric Allylic Substitution with Alkyl
Van Koten, G. et al. Tetrahedron Lett. 1995, 36, 3059
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30 Feringa, B. L. et al. J. Am. Chem. Soc. 2013,135, 2140
Cu-catalyzed allyl−allyl coupling
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Organozinc Reagents
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Seminal Enantioselective Cu-Catalyzed Substitution of Allylic Chlorides
Knochel, P. et al. Angew. Chem. Int. Ed. 1999, 38, 379
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Organoboron Reagents
With Organomagnesium Reagents
With Organoboron Reagents
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Organoboron Reagents
34 Oi, S. et al. Org. Lett. 2012, 14, 4502
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Hayashi, T. et al.
Angew. Chem.
Int. Ed. 2011, 50,
8656
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Summmary
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1)the analogous asymmetric cross-coupling reactions
of tert-alkyl partners represent a largely undeveloped
area
2) provide entry to molecules with all-carbon
quaternary centers
3)few ligands have been shown to support a broad
substrate scope with high selectivity
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Thank you !
Sarash E. Reisman et al. Chem. Rev. ASAP