Record Details

N-Heterocyclic Carbene Catalyzed Asymmetric Intermolecular Stetter Reaction: Origin of Enantioselectivity and Role of Counterions

DSpace at IIT Bombay

View Archive Info
 
 
Field Value
 
Title N-Heterocyclic Carbene Catalyzed Asymmetric Intermolecular Stetter Reaction: Origin of Enantioselectivity and Role of Counterions
 
Creator KUNIYIL, R
SUNOJ, RB
 
Subject MECHANISTIC INSIGHTS
4+2 CYCLOADDITION
ALDOL REACTIONS
GAMMA-LACTAMS
NHC CATALYSIS
STEREOSELECTIVITY
ALDEHYDES
ENALS
 
Description The mechanism and the role of KOtBu in an enantioselective NHC-catalyzed Stetter reaction between p-chlorobenzaldehyde and N-acylamido acrylate is established using DFT(M06-2X) methods. The Gibbs free energies are found to be significantly lower for transition states with explicit bound KOtBu as compared to the conventional pathways without the counterions. An intermolecular proton transfer from HOtBu to the prochiral carbon is identified as the stereocontrolling step. The computed enantioselectivities are in excellent agreement with the experimental results.
 
Publisher AMER CHEMICAL SOC
 
Date 2014-10-16T05:26:05Z
2014-10-16T05:26:05Z
2013
 
Type Article
 
Identifier ORGANIC LETTERS, 15(19)5040-5043
1523-7060
1523-7052
http://dx.doi.org/10.1021/ol402375d
http://dspace.library.iitb.ac.in/jspui/handle/100/15332
 
Language en