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Published August 29, 2012 | Accepted Version + Supplemental Material + Published
Journal Article Open

A Mild, Palladium-Catalyzed Method for the Dehydrohalogenation of Alkyl Bromides: Synthetic and Mechanistic Studies

Abstract

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 L_2PdHBr (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.

Additional Information

© 2012 American Chemical Society. Received: June 28, 2012. Published: August 20, 2012. Support has been provided by the National Institutes of Health (National Institute of General Medical Sciences, Grant R01-GM62871), an American Australian Association Merck Company Foundation Fellowship (A.C.B.), the Paul E. Gray (1954) Endowed Fund for the Undergraduate Research Opportunities Program (A.L.), and the John Reed Fund (A.L.).

Attached Files

Published - ja306323x.pdf

Accepted Version - nihms-402431.pdf

Supplemental Material - ja306323x_si_001.pdf

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Created:
August 19, 2023
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October 20, 2023