Highly selective synthesis of multi-substituted olefins mediated by zirconocene complexes

Keita Hyodo, Yasushi Nishihara

Research output: Contribution to journalArticle

Abstract

In this paper, the efficient methodology for the synthesis of multi-substituted olefins by using zirconocene complexes is described. The key step is regioselective formation of zirconacyclopen-tenes from alkynylboron and alkynylsilane compounds. The subsequent Negishi and Suzuki-Miyaura coupling reactions of C-B and C-Zr bonds give rise to multi-substituted olefins. The developed reaction can be applicable to the synthesis of various functional molecules, for example, an anti-cancer agent. In addition, the mechanism for a regioselective formation of zirconacyclopentenes is analyzed by reactions of alkynylboronates and a zirconocene (II) complex. As a result, it is disclosed that an electrostatic interaction effected the regioselective formation of zirconacyclopen-tenes. The synthesis of various unprecedented tri- and tetra-alkylated olefins using β-hydrogencontaining alkyl electrophiles and alkylzinc reagents as coupling partners in regio- and stereocontrolled manners is also described.

Original languageEnglish
Pages (from-to)792-802
Number of pages11
JournalYuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry
Volume74
Issue number8
Publication statusPublished - 2016

Keywords

  • Boron
  • Carbon-carbon bond formation
  • Cyclic compounds
  • Multi-substituted olefins
  • Silicon
  • Zirconium

ASJC Scopus subject areas

  • Organic Chemistry

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