Rhodium-catalyzed α-methylthiolation reaction of unactivated ketones using 1,2-diphenyl-2-methylthio-1-ethanone for the methylthio transfer reagent

Mieko Arisawa, Fumihiko Toriyama, Masahiko Yamaguchi

Research output: Contribution to journalArticlepeer-review

14 Citations (Scopus)

Abstract

In the presence of catalytic amounts of RhH(PPh3)4, 1,2-bis(diphenylphosphino)ethane (dppe), and dimethyl disulfide, ketones without α-activating groups were α-methylthiolated with 1,2-diphenyl-2-methylthio-1-ethanone giving α-methylthio ketones. The reaction of unsymmetrical ketones proceeded at the more substituted carbons. The initial formation of kinetic α-methylthiolated products followed by their rearrangement to thermodynamic products was observed in the reaction of α-phenyl ketones. Aldehydes, phenylacetate, and phenylacetonitrile were also α-methylthiolated under these conditions.

Original languageEnglish
Pages (from-to)2305-2312
Number of pages8
JournalTetrahedron
Volume67
Issue number12
DOIs
Publication statusPublished - 2011 Mar 25

Keywords

  • C-H activation
  • Equilibrium
  • Ketone
  • Methylthiolation
  • Rhodium catalyst

ASJC Scopus subject areas

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

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