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Allenic Esters from Cyclopropenones by Lewis Base Catalysis: Substrate Scope, the Asymmetric Variant from the Dynamic Kinetic Asymmetric Transformation, and Mechanistic Studies
Author(s) -
Wei Yin,
Zhao WenTao,
Yang YuanLiang,
Zhang Zhen,
Shi Min
Publication year - 2015
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201500466
Subject(s) - chemistry , nucleophile , lewis acids and bases , catalysis , phosphine , kinetic resolution , reaction mechanism , reagent , computational chemistry , substrate (aquarium) , combinatorial chemistry , enantioselective synthesis , organic chemistry , oceanography , geology
The Lewis base catalyzed reactions of cyclopropenones with a variety of nucleophiles (alcohols, phenols, or water) were systematically investigated. We demonstrated that this kind of reaction could be used to synthesize allenic esters in moderate to excellent yields. Furthermore, more synthetically interesting axially chiral allenes in moderate to good yields and ee values were obtained in the corresponding asymmetric reaction in the presence of multifunctional chiral phosphine catalyst. The reaction mechanism was disclosed by using NMR tracing experiments, MS, and DFT calculations. Notably, the asymmetric reaction was proved to be a dynamic kinetic asymmetric transformation based on the control experiments, and the detailed mechanism of this transformation revealed by theoretical investigations.