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Aliphatic Radical Relay Heck Reaction at Unactivated C(sp 3 )−H Sites of Alcohols
Author(s) -
Chuentragool Padon,
Yadagiri Dongari,
Morita Taiki,
Sarkar Sumon,
Parasram Marvin,
Wang Yang,
Gevorgyan Vladimir
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201812398
Subject(s) - chemistry , heck reaction , halogen , halide , alkyl , aryl , catalysis , molecule , combinatorial chemistry , photochemistry , organic chemistry , medicinal chemistry , polymer chemistry
The Mizoroki–Heck reaction is one of the most efficient methods for alkenylation of aryl, vinyl, and alkyl halides. Given 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 allows a Heck reaction to occur at a specific nonfunctionalized C(sp 3 )−H site is desirable. Reported here is a radical relay Heck reaction which allows selective remote alkenylation of aliphatic alcohols at unactivated β‐, γ‐, and δ‐C(sp 3 )−H sites. The use of an easily installed/removed 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.