Rhodium-catalyzed arylthiolation reaction of nitroalkanes, diethyl malonate, and 1,2-diphenylethanone with diaryl disulfides: Control of disfavored equilibrium reaction

Mieko Arisawa, Yuri Nihei, Masahiko Yamaguchi

Research output: Contribution to journalArticlepeer-review

18 Citations (Scopus)

Abstract

In the presence of catalytic amounts of RhH(PPh 3) 4 and 1,2-bis(diphenylphosphino)ethane (dppe), 1-nitroalkanes reacted with a diaryl disulfide giving 1-arylthio-1-nitroalkanes in air. The equilibrium to form thermodynamically disfavored products was shifted by the rhodium-catalyzed oxidation of thiols to disulfides and water. The thiolation reaction of cyclic nitroalkanes proceeded in high yields provided that suitable diaryl disulfides were employed depending on the substrate: di(p-chlorophenyl) disulfide was used for the thiolation reaction of 1-nitroalkanes, 1-nitrocyclopentane and 1-nitrocycloheptane with acidic α-protons (pK a 16 and 17); di(p-methoxyphenyl) disulfide for 1-nitrocyclobutane and 1-nitrocyclohexane with less acidic α-protons (pK a ca. 18). Related reactivities were observed in the thiolation reactions of malonate and 1,2-diphenylethanone.

Original languageEnglish
Pages (from-to)5729-5732
Number of pages4
JournalTetrahedron Letters
Volume53
Issue number43
DOIs
Publication statusPublished - Oct 24 2012
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

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