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A mild, palladium-catalyzed method for the dehydrohalogenation of alkyl bromides: Synthetic and mechanistic studies
journal contribution
posted on 2023-05-17, 19:06 authored by Alexander BissemberAlexander Bissember, Levina, A, Fu, GCWe have exploited a typically undesired elementary step in crosscoupling reactions, β-hydride elimination, to accomplish palladium-catalyzed dehydrohalogenations of alkyl bromides to form terminal olefins. We have applied this method, which proceeds in excellent yield at room temperature in the presence of a variety of functional groups, to a formal total synthesis of (R)-mevalonolactone. Our mechanistic studies have established that the rate-determining step can vary with the structure of the alkyl bromide and, most significantly, that L2PdHBr (L = phosphine), an intermediate that is often invoked in palladium-catalyzed processes such as the Heck reaction, is not an intermediate in the active catalytic cycle.
History
Publication title
Journal of the American Chemical SocietyVolume
134Issue
34Pagination
14232-14237ISSN
0002-7863Department/School
School of Natural SciencesPublisher
American Chemical SocietyPlace of publication
1155 16Th St, Nw, Washington, USA, Dc, 20036Rights statement
Copyright 2012 American Chemical SocietyRepository Status
- Restricted