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Title: Mechanism of metal chloride-promoted mukaiyama aldol reactions
Authors: Chiong, T.W.
Ming, W.W. 
Issue Date: 16-Feb-2007
Citation: Chiong, T.W., Ming, W.W. (2007-02-16). Mechanism of metal chloride-promoted mukaiyama aldol reactions. Journal of Organic Chemistry 72 (4) : 1425-1430. ScholarBank@NUS Repository.
Abstract: (Chemical Equation Presented) Ab initio calculations (MP2/6-311+G**//B3LYP/6-31G*) were employed to investigate the mechanism of metal chloride-promoted Mukaiyama aldol reaction between trihydrosilyl enol ether and formaldehyde. The metal chlorides considered include TiCl4, BCl 3, AlCl3, and GaCl3. In contrast to the concerted pathway of the uncatalyzed aldol reaction, the Lewis acid-promoted reactions favor a stepwise mechanism. Three possible stepwise pathways were located. The lowest energy pathway corresponds to a simultaneous C-C bond formation and a chlorine atom shift in the first (rate-determining) step. This process is calculated to have a low activation barrier of 12 kJ mol-1 for the TiCl4-promoted reaction. The alternative [2+2] cycloaddition and direct carbon-carbon bond formation pathways are energetically competitive. BCl3, AlCl3, and GaCl3 are predicted to be efficient catalysts for the silicon-directed aldol reaction as they strongly activate the formaldehyde electrophile. Formation of a stable pretransition state intermolecular π-π complex between enol silane and the activated formaldehyde (CH2=O⋯MCln) is a key driving force for the facile metal chloride-promoted reactions. © 2007 American Chemical Society.
Source Title: Journal of Organic Chemistry
ISSN: 00223263
DOI: 10.1021/jo062218v
Appears in Collections:Staff Publications

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