Construction of Bridged Polycyclic Systems by Polyene Cyclization

Keisuke Suzuki, Hiroyuki Yamakoshi, Seiichi Nakamura

Research output: Contribution to journalArticlepeer-review

9 Citations (Scopus)

Abstract

A stereoselective construction of bridged tri- and tetracyclic systems embedded in some 3,5-dimethylorsellinic acid (DMOA)-derived meroterpenoids was achieved by exploiting a polyene cyclization of suitably functionalized epoxyallylsilanes. Both the olefinic substituent on the epoxide and allylic trimethylsilyl (TMS) group were found to play pivotal roles in the success of the present reaction. The fact that the cyclization of monocyclized byproducts did not proceed strongly suggests that the reaction could be a concerted transformation. Expansion to bridged compounds: Et2AlCl-promoted polycyclization of epoxyallylsilanes was found to be applicable to the synthesis of bridged tri- and tetracyclic compounds. Five contiguous stereocenters, including three quaternary carbon atoms, were incorporated through internal asymmetric induction in a single operation (see scheme, TMS=trimethylsilyl, Ts=toluenesulfonyl).

Original languageEnglish
Pages (from-to)17605-17609
Number of pages5
JournalChemistry - A European Journal
Volume21
Issue number49
DOIs
Publication statusPublished - 2015 Dec 1
Externally publishedYes

Keywords

  • bioinspired synthesis
  • bridged polycycles
  • cyclization
  • Lewis acids
  • meroterpenoids

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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