Rhodium-Catalyzed Double Dearomatization of 1,2,3-Triazole-Isoxazole Dyads: Synthesis of Nonfused 1H-1,3-Diazepines

A double dearomatization of dyads consisting of 1-sulfonyl-1,2,3-triazoles and 3-aryl-5-methoxyisoxazoles was applied for the efficient synthesis of nonfused 1H-1,3-diazepines. The plausible mechanism of the cascade reaction includes transformation of the 1,2,3-triazole to rhodium azavinyl carbene,...

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Published in:Organic letters 2024-09
Main Authors: Titov, Gleb D, Bunev, Alexander S, Urusova, Svetlana V, Novikov, Mikhail S, Khlebnikov, Alexander F, Rostovskii, Nikolai V
Format: Article
Language:English
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Summary:A double dearomatization of dyads consisting of 1-sulfonyl-1,2,3-triazoles and 3-aryl-5-methoxyisoxazoles was applied for the efficient synthesis of nonfused 1H-1,3-diazepines. The plausible mechanism of the cascade reaction includes transformation of the 1,2,3-triazole to rhodium azavinyl carbene, the Z-selective hydride shift to form the 1-azabuta-1,3-diene moiety, rhodium-catalyzed ring contraction of the isoxazole to azirine, and pseudopericyclic four-atom ring expansion of the azirine. The synthetic utility and antiproliferative activity of the 1,3-diazepines obtained have been demonstrated.A double dearomatization of dyads consisting of 1-sulfonyl-1,2,3-triazoles and 3-aryl-5-methoxyisoxazoles was applied for the efficient synthesis of nonfused 1H-1,3-diazepines. The plausible mechanism of the cascade reaction includes transformation of the 1,2,3-triazole to rhodium azavinyl carbene, the Z-selective hydride shift to form the 1-azabuta-1,3-diene moiety, rhodium-catalyzed ring contraction of the isoxazole to azirine, and pseudopericyclic four-atom ring expansion of the azirine. The synthetic utility and antiproliferative activity of the 1,3-diazepines obtained have been demonstrated.
ISSN:1523-7052
1523-7052
DOI:10.1021/acs.orglett.4c02588