利图菌素类化合物的合成进展：在螺丁烯内酯模板上顺序形成碳-碳键时的立体控制

Progress in the synthesis of the lituarines: stereocontrol in sequential C-C bond formation on a spirobutenolide template.

作者信息

Robertson Jeremy, Dallimore Jonathan W P

机构信息

Department of Chemistry, University of Oxford, Chemistry Research Laboratory, UK.

出版信息

Org Lett. 2005 Oct 27;7(22):5007-10. doi: 10.1021/ol0520018.

DOI:10.1021/ol0520018

PMID:16235944

Abstract

[structure: see text] We describe elaboration of a tricyclic spirobutenolide corresponding to the C(7-18) tricyclic substructure common to lituarines A-C. Conjugate addition, to install the C(16) methyl, is followed by construction of the crucial C(18-19) bond by silyl enol ether addition to the derived spiroacetal C(18)-O oxonium ion. Esterification with a C(1-6) acid, and selective ozonolysis to release the C(23) carbonyl, complete the assembly of all the carbons present in the lituarine macrocyclic core.

摘要

[结构：见正文] 我们描述了一种三环螺丁烯内酯的合成，该内酯对应于石蒜碱A - C共有的C(7 - 18)三环子结构。通过共轭加成引入C(16)甲基，随后通过硅烯醇醚加成到衍生的螺缩醛C(18)-O氧鎓离子上构建关键的C(18 - 19)键。用C(1 - 6)酸进行酯化，并进行选择性臭氧分解以释放C(23)羰基，完成了石蒜碱大环核心中所有碳原子的组装。