Aliphatic Radical Relay Heck Reaction at Unactivated C(sp 3 )−H Sites of Alcohols

Padon Chuentragool, Dongari Yadagiri, Taiki Morita, Sumon Sarkar, Marvin Parasram, Yang Wang, Vladimir Gevorgyan

Research output: Contribution to journalArticlepeer-review

Abstract

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.

Original languageEnglish (US)
Pages (from-to)1794-1798
Number of pages5
JournalAngewandte Chemie - International Edition
Volume58
Issue number6
DOIs
StatePublished - Feb 4 2019

Keywords

  • C−H activation
  • Heck reaction
  • palladium
  • photochemistry
  • radicals

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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