Copper-Catalyzed Aminothiolation of 1,3-Dienes via a Dihydrothiazine Intermediate

Christopher E. Sleet, Uttam K. Tambar

Research output: Contribution to journalArticle

11 Scopus citations

Abstract

Heteroatom-containing organic molecules are of particular interest to medicinal chemists and materials scientists. A strategy to reach these architectures via direct difunctionalization of abundant 1,3-dienes is especially attractive. Herein, we describe the development of a regio- and diastereoselective 1,4-aminothiolation of 1,3-dienes with a sulfur diimide reagent, a copper catalyst, and alkyl Grignard reagents. This unique protocol provides remote nitrogen and sulfur functionalities with high levels of stereocontrol. The reaction proceeds via a tandem hetero-Diels–Alder cycloaddition of N,N′-bis(benzenesulfonyl)sulfur diimide with 1,3-diene followed by copper-catalyzed Grignard substitution. Mechanistic studies support a copper catalyzed formation of an unprecedented [10-S-4] sulfurane that reductively eliminates to afford a 3,6-dihydrothiazine, which is selectively converted to 1,4-aminothiols.

Original languageEnglish (US)
Pages (from-to)5536-5540
Number of pages5
JournalAngewandte Chemie - International Edition
Volume56
Issue number20
DOIs
StatePublished - Jan 1 2017

Keywords

  • copper
  • cycloaddition
  • nitrogen
  • sulfur
  • sulfur heterocycles

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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