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The Mechanism of the Stetter Reaction - A DFT Study


Hawkes, KJ and Yates, BF, The Mechanism of the Stetter Reaction - A DFT Study, European Journal of Organic Chemistry, 2008, (33) pp. 5563-5570. ISSN 1434-193X (2008) [Refereed Article]

DOI: doi:10.1002/ejoc.200800506


On the basis of Breslow's mechanism for benzoin condensation, a model asymmetric Stetter reaction has been investigated using DFT methods. In contrast to the concerted benzoin condensation, after formation of the Breslow intermediate the Stetter reaction is found to be a two-step process in which the rate-determining C-C coupling of the Breslow intermediate and the Michael acceptor precedes final proton transfer. In addition, the enolamine is found to play a significant role in the stereochemistry of the product, with the energy difference between stereoisomers of this intermediate reflected throughout the remainder of the reaction sequence. Consequently, electronic and steric control of the stereochemistry of this intermediate should directly enhance the ee values of the product. © Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Organic chemistry
Research Field:Physical organic chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding knowledge
Objective Field:Expanding knowledge in the chemical sciences
UTAS Author:Hawkes, KJ (Dr Kirsty Hawkes)
UTAS Author:Yates, BF (Professor Brian Yates)
ID Code:55272
Year Published:2008
Web of Science® Times Cited:70
Deposited By:Chemistry
Deposited On:2009-03-08
Last Modified:2012-03-05

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