Disilametallacyclic chemistry for efficient catalysis

Yusuke Sunada, Hideo Nagashima

研究成果: ジャーナルへの寄稿評論記事

11 引用 (Scopus)

抄録

This article discusses two new features of disilametallacyclic chemistry that contribute to the development of efficient catalytic reactions in organic synthesis. The first is disilametallacyclic intermediates in the hydrosilane reduction of carbonyl compounds. Experimental and theoretical studies on disilaplatinacycles suggested that the H 2 Pt(iv)Si 2 species generated by oxidative addition of 1,2-bis(dimethylsilyl)benzene behaves as a highly reactive hydride to reduce amides to amines. This mechanism via disilametallacyclic intermediates explains the efficient hydrosilane reduction of carbonyl compounds with α,ω-bifunctional hydrosilanes catalyzed by other transition metals. The second is hydrogenation of alkenes by disilaferra- or disilaruthenacyclic complexes as catalyst precursors. A new mechanism not involving the conventional oxidative addition of H 2 was suggested from DFT calculations, in which activation of the H-H bond occurs in the metal-silicon bond of the disilametallacyclic intermediate. Disilametallacyclic intermediates contribute to efficient catalytic reactions through this σ-CAM (σ-complex assisted mechanism) type mechanism.

元の言語英語
ページ(範囲)7644-7655
ページ数12
ジャーナルDalton Transactions
46
発行部数24
DOI
出版物ステータス出版済み - 1 1 2017

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Carbonyl compounds
Catalysis
Alkenes
Silicon
Benzene
Discrete Fourier transforms
Amides
Hydrides
Hydrogenation
Amines
Transition metals
Metals
Chemical activation
Catalysts

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

これを引用

Disilametallacyclic chemistry for efficient catalysis. / Sunada, Yusuke; Nagashima, Hideo.

:: Dalton Transactions, 巻 46, 番号 24, 01.01.2017, p. 7644-7655.

研究成果: ジャーナルへの寄稿評論記事

Sunada, Yusuke ; Nagashima, Hideo. / Disilametallacyclic chemistry for efficient catalysis. :: Dalton Transactions. 2017 ; 巻 46, 番号 24. pp. 7644-7655.
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