Allenic Esters from Cyclopropenones by Lewis Base Catalysis: Substrate Scope, the Asymmetric Variant from the Dynamic Kinetic Asymmetric Transformation, and Mechanistic Studies

Allenic Esters from Cyclopropenones by Lewis Base Catalysis: Substrate Scope, the Asymmetric Variant from the Dynamic Kinetic Asymmetric Transformation, and Mechanistic Studies

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...

Full description

Saved in:
Bibliographic Details
Published in:ChemCatChem 2015-10, Vol.7 (20), p.3340-3349
Main Authors: Wei, Yin, Zhao, Wen-Tao, Yang, Yuan-Liang, Zhang, Zhen, Shi, Min
Format: Article
Language:eng
Subjects:
allenes
asymmetric catalysis
chirality
cyclopropenone
Lewis bases
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary: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. Axially chiral allenes: The reactions of cyclopropenones with a variety of nucleophiles are catalyzed by different Lewis bases, affording the allenic esters in moderate to excellent yields. Axially chiral allenes are given in moderate to good yields and ee values, catalyzed by multifunctional chiral phosphines in a dynamic kinetic asymmetric transformation. The reaction mechanism is disclosed through NMR tracing experiments, MS, and DFT calculations. CP*=Chiral phosphine.
ISSN:1867-3880
1867-3899