Premium
Isomerization of Olefins Triggered by Rhodium‐Catalyzed CH Bond Activation: Control of Endocyclic β‐Hydrogen Elimination
Author(s) -
Yip Stephanie Y. Y.,
Aïssa Christophe
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201500596
Subject(s) - isomerization , rhodium , chemistry , decarbonylation , catalysis , medicinal chemistry , hydrogen , double bond , photochemistry , organic chemistry
Five‐membered metallacycles are typically reluctant to undergo endocyclic β‐hydrogen elimination. The rhodium‐catalyzed isomerization of 4‐pentenals into 3‐pentenals occurs through this elementary step and cleavage of two CH bonds, as supported by deuterium‐labeling studies. The reaction proceeds without decarbonylation, leads to trans olefins exclusively, and tolerates other olefins normally prone to isomerization. Endocyclic β‐hydrogen elimination can also be controlled in an enantiodivergent reaction on a racemic mixture.