Alkenylation and Allylation Reactions of Alkyl Halides Using Photo Catalyst

Shuhei Sumino, Ilhyong Ryu

    Research output: Contribution to journalArticlepeer-review

    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 - May 2019

    Keywords

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

    Fingerprint

    Dive into the research topics of 'Alkenylation and Allylation Reactions of Alkyl Halides Using Photo Catalyst'. Together they form a unique fingerprint.

    Cite this