Premium
Cationic Iridium/Chiral Bisphosphine‐Catalyzed Enantioselective Hydroacylation of Ketones
Author(s) -
Shirai Tomohiko,
Iwasaki Tomoya,
Kanemoto Kazuya,
Yamamoto Yasunori
Publication year - 2020
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.202000386
Subject(s) - hydroacylation , enantioselective synthesis , iridium , cationic polymerization , catalysis , chemistry , organic chemistry , polymer chemistry , rhodium
A facile and convenient synthesis of the chiral phthalide framework catalyzed by cationic iridium was developed. The method utilized cationic iridium/bisphosphine‐catalyzed asymmetric intramolecular carbonyl hydroacylation of 2‐keto benzaldehydes to furnish the corresponding optically active phthalide products in good to excellent enantioselectivities (up to 98% ee ). The mechanistic studies using a deuterium‐labelled substrate suggested that the reaction involved an intramolecular carbonyl insertion mechanism to iridium hydride intermediate. In addition, we investigated the kinetic isotope effect (KIE) of intramolecular hydroacylation with deuterated substrate and determined that the C−H activation step is not included in the turnover‐limiting step.