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Issue 10, 2021
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Structural elucidation of a methylenation reagent of esters: synthesis and reactivity of a dinuclear titanium(iii) methylene complex

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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.

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

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Article information


Submitted
20 Nov 2020
Accepted
19 Jan 2021
First published
19 Jan 2021

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2021,12, 3509-3515
Article type
Edge Article

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

T. Kurogi, K. Kuroki, S. Moritani and K. Takai, Chem. Sci., 2021, 12, 3509
DOI: 10.1039/D0SC06366E

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