Alkenylation and allylation reactions of alky I Ha I ides using photo catalyst

Shuhei Sumino, Ilhyong Ryu

Research output: Contribution to journalArticle

Abstract

Radical addition/β-fragmentation sequence has long been utilized for alkenylation and allylation of alkyl halides, in which key alkyl radicals are generated from alkyl halides by SH2 reaction typically using tributyltin radical. In this article, we describe modernized alkenylation and allylation of alkyl halides, in which alkyl radical generation is carried out by electron transfer under photoirradiation with the use of transition metal catalyst, which enables us to carry out the radical alkenylation and allylation without the use of radical initiators nor chain transfer reagents. Indeed, radical alkenylation of alkyl iodides using alkenyl bromides proceeded well by the use of a Pd/light combined system involving Hantzsch ester. Alkenyl and allyl sulfones worked better, since the system can obviate the use of Hantzsch ester. Mechanistically spontaneous reductive elimination of PhSCM is suggested to recover the Pd catalyst. We also discuss allylation of gem-difluoromethy-lene-containing alkyl halides using allyl sulfones. which is best performed by the use of a visible light photoredox system based on Ru-catalyst.

Original languageEnglish
Pages (from-to)406-413
Number of pages8
JournalYuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry
Volume77
Issue number5
DOIs
StatePublished - 1 Jan 2019

Keywords

  • Addition/ß-fragmentation
  • Alkenylation
  • Allylation
  • Electron-transfer
  • Photo catalyst
  • Radical

Fingerprint Dive into the research topics of 'Alkenylation and allylation reactions of alky I Ha I ides using photo catalyst'. Together they form a unique fingerprint.

  • Cite this