Biogenetically inspired synthesis and skeletal diversification of indole alkaloids

• Mizoguchi, Haruki

• Oikawa, Hideaki

• Oguri, Hiroki

抄録

To access architecturally complex natural products, chemists usually devise a customized synthetic strategy for constructing a single target skeleton. In contrast, biosynthetic assembly lines often employ divergent intramolecular cyclizations of a polyunsaturated common intermediate to produce diverse arrays of scaffolds. With the aim of integrating such biogenetic strategies, we show the development of an artificial divergent assembly line generating unprecedented numbers of scaffold variations of terpenoid indole alkaloids. This approach not only allows practical access to multipotent intermediates, but also enables systematic diversification of skeletal, stereochemical and functional group properties without structural simplification of naturally occurring alkaloids. Three distinct modes of [412] cyclizations and two types of redox-mediated annulations provided divergent access to five skeletally distinct scaffolds involving iboga-, aspidosperma-, andranginine- and ngouniensine-type skeletons and a non-natural variant within six to nine steps from tryptamine. The efficiency of our approach was demonstrated by successful total syntheses of (+/-)-vincadifformine, (+/-)-andranginine and (2)-catharanthine.

収録刊行物

• Nature chemistry

  Nature chemistry 6 (1), 57-64, 2014-01

  Nature publishing group

詳細情報

• CRID: 1050564288969055744
• NII論文ID: 120005476195
• HANDLE: 2115/57295
• ISSN: 17554330
• 本文言語コード: en
• 資料種別: journal article
• データソース種別:
  • IRDB
  • CiNii Articles