Structural elucidation of a methylenation reagent of esters: synthesis and reactivity of a dinuclear titanium(iii) methylene complex |
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| Authors: | Takashi Kurogi Kaito Kuroki Shunsuke Moritani Kazuhiko Takai |
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| Institution: | Division of Applied Chemistry, Graduate School of National Science and Technology, Okayama University, 3-1-1 Tsushimanaka, Kita-ku, Okayama 700-8530 Japan, |
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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.Transmetallation of a zinc methylene complex ZnI(tmeda)]2(μ-CH2) with a titanium(iii) chloride TiCl3(tmeda)(thf)] produced a titanium methylene complex. |
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