柯蒲木生物碱（±）-lapidilectine B的全合成

Total synthesis of the Kopsia lapidilecta alkaloid (+/-)-lapidilectine B.

作者信息

Pearson William H, Lee Ill Young, Mi Yuan, Stoy Patrick

机构信息

Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109-1055 USA.

出版信息

J Org Chem. 2004 Dec 24;69(26):9109-22. doi: 10.1021/jo048917u.

DOI:10.1021/jo048917u

PMID:15609944

Abstract

The total synthesis of Kopsia lapidilecta alkaloid (+/-)-lapidilectine B is described. Notable elements of this synthesis include the first natural products application of the Smalley azido-enolate cyclization to form the 1,2-dihydro-3H-indol-3-one (indoxyl) core and installation of the pyrrolidine ring by a 2-azaallyllithium [3+2] cycloaddition with the acetylene equivalent phenyl vinyl sulfide. Closure of the eight-membered perhydroazocine ring is accomplished via the intramolecular S(N)2 substitution of a mesylate. This constitutes the first synthesis of a member of the 5,6,12,13-tetrahydro-11a,13a-ethano-3H-pyrrolo[1',2':1,8]azocino[5,4-b]indole class of alkaloids.

摘要

描述了柯蒲木生物碱（±）-lapidilectine B的全合成。该合成的显著特点包括首次将斯莫利叠氮烯醇化物环化应用于天然产物，以形成1,2-二氢-3H-吲哚-3-酮（吲哚酚）核心，并通过与乙炔等效物苯乙烯基硫醚进行2-氮杂烯丙基锂[3+2]环加成来安装吡咯烷环。八元全氢氮杂辛环的闭合是通过甲磺酸酯的分子内S(N)2取代完成的。这是5,6,12,13-四氢-11a,13a-亚乙基-3H-吡咯并[1',2':1,8]氮杂辛并[5,4-b]吲哚类生物碱成员的首次合成。