Titov Gleb D, Bunev Alexander S, Urusova Svetlana V, Novikov Mikhail S, Khlebnikov Alexander F, Rostovskii Nikolai V
St. Petersburg State University, Institute of Chemistry, Saint Petersburg 199034, Russia.
Togliatti State University, Medicinal Chemistry Center, Togliatti 445020, Russia.
Org Lett. 2024 Sep 20;26(37):7828-7833. doi: 10.1021/acs.orglett.4c02588. Epub 2024 Sep 6.
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 1-1,3-diazepines. The plausible mechanism of the cascade reaction includes transformation of the 1,2,3-triazole to rhodium azavinyl carbene, the -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.
由1-磺酰基-1,2,3-三唑和3-芳基-5-甲氧基异恶唑组成的二元体系的双重脱芳构化反应被用于高效合成非稠合的1,1,3-二氮杂䓬。该串联反应的可能机理包括1,2,3-三唑转化为铑氮杂乙烯基卡宾、选择性氢迁移形成1-氮杂丁-1,3-二烯部分、铑催化异恶唑环收缩为氮丙啶以及氮丙啶的拟周环四原子环扩展。所得到的1,3-二氮杂䓬的合成效用和抗增殖活性已得到证实。
