The Mechanism of the Stetter Reaction - A DFT Study
journal contribution
posted on 2023-05-16, 23:11 authored by Kirsty HawkesKirsty Hawkes, Brian YatesBrian YatesOn 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.
History
Publication title
European Journal of Organic ChemistryVolume
2008Issue
33Pagination
5563-5570ISSN
1434-193XDepartment/School
School of Natural SciencesPublisher
Wiley VCHPlace of publication
WeinheimRepository Status
- Restricted
Socio-economic Objectives
Expanding knowledge in the chemical sciencesUsage metrics
Categories
Keywords
Licence
Exports
RefWorksRefWorks
BibTeXBibTeX
Ref. managerRef. manager
EndnoteEndnote
DataCiteDataCite
NLMNLM
DCDC