A Mild, Palladium-Catalyzed Method for the Dehydrohalogenation of Alkyl Bromides: Synthetic and Mechanistic Studies
Author(s)
Bissember, Alex C.; Levina, Anna; Fu, Gregory C.
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We have exploited a typically undesired elementary step in cross-coupling 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.
Date issued
2012-08Department
Massachusetts Institute of Technology. Department of ChemistryJournal
Journal of the American Chemical Society
Publisher
American Chemical Society
Citation
Bissember, Alex C., Anna Levina, and Gregory C. Fu. “A Mild, Palladium-Catalyzed Method for the Dehydrohalogenation of Alkyl Bromides: Synthetic and Mechanistic Studies.” Journal of the American Chemical Society 134, no. 34 (August 29, 2012): 14232-14237.
Version: Author's final manuscript
ISSN
0002-7863
1520-5126