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Catalytic, Enantioselective, Vinylogous Aldol Reactions
Author(s) -
Denmark Scott E.,
Heemstra John R.,
Beutner Gregory L.
Publication year - 2005
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.200462338
Subject(s) - enantioselective synthesis , aldol reaction , electrophile , nucleophile , chemistry , functional group , double bond , catalysis , stereochemistry , organic chemistry , polymer
Abstract In 1935, R. C. Fuson formulated the principle of vinylogy to explain how the influence of a functional group may be felt at a distant point in the molecule when this position is connected by conjugated double‐bond linkages to the group. In polar reactions, this concept allows the extension of the electrophilic or nucleophilic character of a functional group through the π system of a carbon–carbon double bond. This vinylogous extension has been applied to the aldol reaction by employing “extended” dienol ethers derived from γ‐enolizable α,β‐unsaturated carbonyl compounds. Since 1994, several methods for the catalytic, enantioselective, vinylogous aldol reaction have appeared, with which varying degrees of regio‐ (site), enantio‐, and diastereoselectivity can be attained. In this Review, the current scope and limitations of this transformation, as well as its application in natural product synthesis, are discussed.