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Metalated Nitriles: Internal 1,3‐Asymmetric Induction
Author(s) -
Fleming Fraser F.,
Liu Wang
Publication year - 2009
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200801053
Subject(s) - chemistry , electrophile , stereoselectivity , steric effects , stereocenter , nitrile , nucleophile , stereochemistry , carbanion , asymmetric induction , combinatorial chemistry , organic chemistry , enantioselective synthesis , catalysis
Stereoselective alkylations of acyclic, metalated nitriles are intimately controlled by a remote stereocenter. Probing the optimal steric demand through alkylations with a series of substituted pentanenitriles reveal the fundamental requirements for 1,3‐asymmetric induction. Relaying these requirements into a predictive model suggests that the stereoselectivity arises from a preferential electrophilic attack on the more stable diamond lattice conformation of the metalated nitrile. Using this strategy a series of metalated alkanenitriles selectively intercept a diverse range of electrophiles in alkylations that efficiently install new quaternary centers. The metalated nitrile alkylations provide fundamental insight for remote stereoinduction and a solid foundation for further advances in stereoselective alkylations of flexible nucleophiles having a defined shape.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)