Structural elucidation of a methylenation reagent of esters: Synthesis and reactivity of a dinuclear titanium(iii) methylene complex

Takashi Kurogi, Kaito Kuroki, Shunsuke Moritani, Kazuhiko Takai

Research output: Contribution to journalArticlepeer-review

Abstract

Transmetallation of a zinc methylene complex [ZnI(tmeda)]2(μ-CH2) with a titanium(iii) chloride [TiCl3(tmeda)(thf)] produced a titanium methylene complex. The X-ray diffraction study displayed a dinuclear methylene structure [TiCl(tmeda)]2(μ-CH2)(μ-Cl)2. Treatment of an ester with the titanium methylene complex resulted in methylenation of the ester carbonyl to form a vinyl ether. The titanium methylene complex also reacted with a terminal olefin, resulting in olefin-metathesis and olefin-homologation. Cyclopropanation by methylene transfer from the titanium methylene proceeded by use of a 1,3-diene. The mechanistic study of the cyclopropanation reaction by the density functional theory calculations was also reported.

Original languageEnglish
Pages (from-to)3509-3515
Number of pages7
JournalChemical Science
Volume12
Issue number10
DOIs
Publication statusPublished - Mar 14 2021

ASJC Scopus subject areas

  • Chemistry(all)

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