Intermolecular C−H Activation at the Allylic/Benzylic and Homoallylic/Homobenzylic Positions of Cyclic Hydrocarbons by a Stable Divalent Silicon Species

Taichi Koike, Tomoyuki Kosai, Takeaki Iwamoto

Research output: Contribution to journalArticlepeer-review

Abstract

Direct activation of inert C(sp3)−H bonds by main group element species is yet a formidable challenge. Herein, the dehydrogenation of cyclohexene and 1,2,3,4-tetrahydronaphthalene through the allylic/benzylic and homoallylic/homobenzylic C−H bond activation by cyclic (alkyl)(amino)silylene 1 in neat conditions is reported to yield the corresponding aromatic compounds. As for the reaction of cyclohexene, allylsilane 3 and 7-silanorbornene 4 were also observed, which could be interpreted as a direct dehydrogenative silylation reaction of monoalkenes at the allylic positions. Experimental and computational studies suggest that the dehydrogenation of cyclohexene at the homoallylic position was accomplished by a combination of silylene 1 and radical intermediates such as hydrosilyl radical INT1 or cyclohexenyl radical H, which are generated in the initial step of the reaction.

Original languageEnglish
Pages (from-to)724-734
Number of pages11
JournalChemistry - A European Journal
Volume27
Issue number2
DOIs
Publication statusPublished - 2021 Jan 7

Keywords

  • C−H activation
  • carbene homologues
  • dehydrogenation
  • homoallylic
  • silylation

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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