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Aliphatic Radical Relay Heck Reaction at Unactivated C(sp3)–H Sites of Alcohols

preprint
submitted on 19.09.2018 and posted on 20.09.2018 by Padon Chuentragool, Dongari Yadagiri, Taiki Morita, Sumon Sarkar, Marvin Parasram, Yang Wang, Vladimir Gevorgyan
The Mizoroki−Heck reaction is one of the most efficient methods for alkenylation of
aryl, vinyl, and alkyl halides. Due to its innate nature, this protocol requires the employment of compounds possessing a halogen atom at the site of functionalization. However, the accessibility of organic molecules possessing a halogen atom at a particular site in aliphatic systems is extremely limited. Thus, a protocol that would allow a Heck reaction to occur at a specific non-functionalized C(sp3)−H site would be highly desirable.
Here, we report a radical relay Heck reaction which allows for a selective remote
alkenylation of aliphatic alcohols at unactivated β-, γ- and δ-C(sp3 20 )–H sites. The use of easily installable/removable Si-based auxiliary enables selective I-atom/radical translocation events at remote C−H sites followed by the Heck reaction. Notably, the reaction proceeds smoothly under mild visible light-mediated conditions at room temperature, producing highly modifiable and valuable alkenol products from readily available alcohols feedstocks.

Funding

NIH GM120281, NSF CHE-1663779

History

Email Address of Submitting Author

vlad@uic.edu

Institution

University of Illinois at Chicago

Country

United States

ORCID For Submitting Author

0000-0002-7836-7596

Declaration of Conflict of Interest

none

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in Angewandte Chemie International Edition

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