TY - JOUR

T1 - Rhodium-Catalyzed Double Dearomatization of 1,2,3-Triazole−Isoxazole Dyads: Synthesis of Nonfused 1H‑1,3-Diazepines

AU - Ростовский, Николай Витальевич

AU - Хлебников, Александр Феодосиевич

AU - Новиков, Михаил Сергеевич

AU - Титов, Глеб Денисович

AU - Урусова, Светлана Владимировна

AU - Бунев, Александр Сиясатович

PY - 2024/9/6

Y1 - 2024/9/6

N2 - 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.

AB - 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.

M3 - Article

VL - 26

SP - 7828−7833

JO - Organic Letters

JF - Organic Letters

SN - 1523-7060

IS - 37

ER -