Please use this identifier to cite or link to this item:
Title: Facile uncatalyzed Mukaiyama aldol reactions: An ab initio study of the effects of substituents
Authors: Chiong, T.W.
Ming, W.W. 
Issue Date: 7-Jan-2005
Citation: Chiong, T.W., Ming, W.W. (2005-01-07). Facile uncatalyzed Mukaiyama aldol reactions: An ab initio study of the effects of substituents. Journal of Organic Chemistry 70 (1) : 124-131. ScholarBank@NUS Repository.
Abstract: (Chemical Equation Presented). High-level ab initio molecular orbital calculations at the G3(MP2) level of theory were carried out to investigate the effects of substituents on the energetics of the uncatalyzed Mukaiyama aldol reaction between trihydrosilyl enol ether and formaldehyde. The concerted pathway, via a twist-boat six-membered ring transition state, is strongly favored over the stepwise pathway which involves a four-membered ring oxetane intermediate. Six substituents (CH3, NH2, OH, F, SH, and CHO) on trihydrosilyl enol ether and eight substituents (CH3, CF 3, NH2, F, CHO, COOCH3, CH= CH2, and C6H5) on formaldehyde were considered. We find that the reaction exothermicity is the main factor that dominates reactivity. The calculated barriers vary considerably from 30 to 131 kJ mol-1. With the exception of halogen substitution, the nucleophilicity of silyl enol ether and the electrophilicity of the aldehyde are important in promoting the reactivity of this class of aldol addition. The roles of frontier molecular orbital interactions and electrostatic interactions are also discussed. In addition, our study has revealed that employing substituents on both reactants can act in a cooperatively manner to reduce the activation barrier further. In particular, we predict that the reactions between NH2-substituted enol silane and CHO-, COOCH3-, and CF3-substituted aldehydes have remarkably low barriers (
Source Title: Journal of Organic Chemistry
ISSN: 00223263
DOI: 10.1021/jo048398v
Appears in Collections:Staff Publications

Show full item record
Files in This Item:
There are no files associated with this item.


checked on Mar 20, 2019


checked on Mar 20, 2019

Page view(s)

checked on Mar 16, 2019

Google ScholarTM



Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.