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Highly Enantioselective Rhodium(I)‐Catalyzed Carbonyl Carboacylations Initiated by CC Bond Activation
Author(s) -
Souillart Laetitia,
Cramer Nicolai
Publication year - 2014
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.201405834
Subject(s) - hydroacylation , chemistry , aldehyde , rhodium , enantioselective synthesis , ketone , catalysis , medicinal chemistry , alkyl , carbonyl group , hydride , stereochemistry , organic chemistry , hydrogen
The lactone motif is ubiquitous in natural products and pharmaceuticals. The Tishchenko disproportionation of two aldehydes, a carbonyl hydroacylation, is an efficient and atom‐economic access to lactones. However, these reaction types are limited to the transfer of a hydride to the accepting carbonyl group. The transfer of alkyl groups enabling the formation of CC bonds during the ester formation would be of significant interest. Reported herein is such asymmetric carbonyl carboacylation of aldehydes and ketones, thus affording complex bicyclic lactones in excellent enantioselectivities. The rhodium(I)‐catalyzed transformation is induced by an enantiotopic CC bond activation of a cyclobutanone and the formed rhodacyclic intermediate reacts with aldehyde or ketone groups to give highly functionalized lactones.