Iron-Induced regio- and stereoselective addition of sulfenyl chlorides to alkynes by a radical pathway

Masayuki Iwasaki, Tomoya Fujii, Kiyohiko Nakajima, Yasushi Nishihara

Research output: Contribution to journalArticle

50 Citations (Scopus)

Abstract

The radical addition of the ClS s-bond in sulfenyl chlorides to various C~C triple bonds has been achieved with excellent regio- and stereoselectivity in the presence of a catalytic amount of a common iron salt. The reaction is compatible with a variety of functional groups and can be scaled up to the gram-scale with no loss in yield. As well as terminal alkynes, internal alkynes underwent stereodefined chlorothiolation to provide tetrasubstituted alkynes. Preliminary mechanistic investigations revealed a plausible radical process involving a sulfur-centered radical intermediate via iron-mediated homolysis of the ClS bond. The resulting chlorothiolation adducts can be readily transformed to the structurally complex alkenyl sulfides by cross-coupling reactions. The present reaction can also be applied to the complementary synthesis of the potentially useful bis-sulfoxide ligands for transition-metal-catalyzed reactions.

Original languageEnglish
Pages (from-to)13880-13884
Number of pages5
JournalAngewandte Chemie - International Edition
Volume53
Issue number50
DOIs
Publication statusPublished - Oct 15 2014

Fingerprint

Alkynes
Chlorides
sulfoxide
Iron
Stereoselectivity
Regioselectivity
Functional groups
Transition metals
Sulfur
Ligands
Sulfides
Salts

Keywords

  • Alkynes
  • Chlorothiolation
  • Iron
  • Radical reactions
  • Synthetic methods

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis

Cite this

Iron-Induced regio- and stereoselective addition of sulfenyl chlorides to alkynes by a radical pathway. / Iwasaki, Masayuki; Fujii, Tomoya; Nakajima, Kiyohiko; Nishihara, Yasushi.

In: Angewandte Chemie - International Edition, Vol. 53, No. 50, 15.10.2014, p. 13880-13884.

Research output: Contribution to journalArticle

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