Copper-Catalyzed Aminothiolation of 1,3-Dienes via a Dihydrothiazine Intermediate |
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Authors: | Christopher E Sleet Prof Uttam K Tambar |
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Institution: | Department of Biochemistry, The University of Texas Southwestern Medical Center, 5323 Harry Hines Boulevard, Dallas, TX, 75390-9038 USA |
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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. |
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Keywords: | Cycloadditionen Kupfer Schwefel Schwefelheterocyclen Stickstoff |
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