Hong Xuechuan, France Stefan, Padwa Albert
Department of Chemistry, Emory University, Atlanta, GA 30322, USA.
Tetrahedron. 2007 Jun 25;63(26):5962-5976. doi: 10.1016/j.tet.2007.01.064.
Using a metal-catalyzed domino reaction as the key step, the heterocyclic skeleton of the kopsifoline alkaloid family was constructed by a 1,3-dipolar cycloaddition of a carbonyl ylide dipole derived from a Rh(II)-catalyzed reaction of a diazo ketoester across the indole pi-bond. Ring opening of the resulting 1,3-dipolar cycloadduct followed by a reductive dehydroxylation step resulted in the formation of a critical silyl enol ether necessary for the final F-ring closure of the kopsifoline skeleton.
以金属催化的多米诺反应为关键步骤，通过重氮酮酯经铑（II）催化反应生成的羰基叶立德偶极体与吲哚π键进行1,3-偶极环加成反应，构建了柯蒲木碱生物碱家族的杂环骨架。所得1,3-偶极环加成产物开环，随后经过还原脱羟基步骤，生成了柯蒲木碱骨架最终F环闭合所必需的关键硅烯醇醚。
