Premium
Enantioselective Synthesis of ( E )‐δ‐Boryl‐Substituted anti ‐Homoallylic Alcohols Using Palladium and a Chiral Phosphoric Acid
Author(s) -
Miura Tomoya,
Nakahashi Junki,
Murakami Masahiro
Publication year - 2017
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.201702611
Subject(s) - palladium , isomerization , phosphoric acid , chemistry , enantioselective synthesis , catalysis , selectivity , double bond , medicinal chemistry , organic chemistry
Abstract ( E )‐δ‐Boryl‐substituted anti ‐homoallylic alcohols are synthesized in a highly diastereo‐ and enantioselective manner from 1,1‐di(boryl)alk‐3‐enes and aldehydes. Mechanistically, the reaction consists of 1) palladium‐catalyzed double‐bond transposition of the 1,1‐di(boryl)alk‐3‐enes to 1,1‐di(boryl)alk‐2‐enes, 2) chiral phosphoric acid catalyzed allylation of aldehydes, and 3) palladium‐catalyzed geometrical isomerization from the Z to E isomer. As a result, the configurations of two chiral centers and one double bond are all controlled with high selectivity in a single reaction vessel.