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

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.

SUBMITTER: Sleet CE

PROVIDER: S-EPMC5668140 | biostudies-literature | 2017 May

REPOSITORIES: biostudies-literature

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

Sleet Christopher E CE Tambar Uttam K UK

Angewandte Chemie (International ed. in English) 20170413 20

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 hig ...[more]

PMID: 28407352

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