Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 61, Issue 19, Pages -Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202201151
Keywords
Carbenes; Cobalt(II)/N,N'-Dioxide; Thiiranes; Thioketones; alpha-Diazo Compounds
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Funding
- National Natural Science Foundation of China [22188101]
- Sichuan University [2020SCUNL204]
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This study reports the enantioselective cycloaddition reaction between thioketones and alpha-diazo pyrazoleamides, leading to the direct synthesis of tetrasubstituted thiiranes, which can be further transformed into tetrasubstituted olefins through desulfuration. The reaction is catalyzed by chiral N,N'-dioxide/cobalt(II) complexes and exhibits high efficiency and stereoselectivity. This work provides a route for selectively constructing challenging compounds.
Herein, we report the first example of enantioselective (2+1) cycloaddition of thioketones with alpha-diazo pyrazoleamides for the direct synthesis of tetrasubstituted thiiranes. In the presence of chiral N,N'-dioxide/cobalt(II) complexes (2-5 mol%), excellent efficiency (up to 99% yield within 15 mins) and high stereoselectivity (up to > 19: 1 dr and 97% ee) are available. Elaborations of thiiranes via desulfuration have also been conducted to deliver tetrasubstituted olefins. Density functional theory calculations reveal that the reaction initiates from a doublet state cobalt(II) carbenoid, which is followed by a quartet cobalt(II)-bound thiocarbonyl ylide pathway. This work provides a route for the selective construction of tetrasubstituted thiiranes and olefins that are otherwise difficult to access.
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