Synthesis and Unique Catalytic Reactivity of Metal Complexes with Chelate-Type Silyl Ligands Connected by Xanthene
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- Tobita Hiromi
- Department of Chemistry, Graduate School of Science, Tohoku University
Bibliographic Information
- Other Title
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- キサンテンで連結されたキレート型シリル配位子をもつ金属錯体の合成と特異な触媒作用
- キサンテン デ レンケツ サレタ キレートガタ シリル ハイイシ オ モツ キンゾク サクタイ ノ ゴウセイ ト トクイ ナ ショクバイ サヨウ
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Abstract
<p>Design and synthesis of supporting ligands for transition-metal complexes are significant as an efficient method for development of new metal complex catalysts for organic synthesis. Metal complexes bearing chelate-type silyl supporting ligands are expected to show high catalytic performance toward activation of inert bonds such as C-H due to the strongly σ-donating and trans-labilizing properties of their silyl ligand moieties. This article describes recent progress of synthesis and catalysis of transition-metal complexes bearing a xanthene-based bis(silyl)supporting ligand “xantsil”, developed by our previous study, and a related silyl(phosphine)-xanthene chelate ligand “xantSiP”. These complexes were synthesized straightforwardly by reactions of (hydrosilyl)xanthene derivatives as ligand precursors with low-valent metal complexes via Si-H activation and ligand substitution. As a prominent result, the reaction of arylalkynes with hydrosilanes catalyzed by 16-electron ruthenium-xantsil complexes with bulky trialkylphosphine was found to give 2-silylstyrenes via ortho-C-H silylation and trans-selective hydrogenation (ortho-C-H silylation/hydrogenation). On the other hand, when catalysts with triaminophosphine instead of trialkylphosphine were used for the reaction, 2,α-bis(silyl)styrenes were formed in most cases via ortho-C-H silylation and trans-selective hydrosilylation (ortho-C-H silylation/hydrosilylation). These novel C-H silylation reactions proceeded under mild conditions(room temp.∼70 °C).</p>
Journal
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- Journal of Synthetic Organic Chemistry, Japan
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Journal of Synthetic Organic Chemistry, Japan 76 (12), 1301-1309, 2018-12-01
The Society of Synthetic Organic Chemistry, Japan
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Details 詳細情報について
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- CRID
- 1390845713030079360
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- NII Article ID
- 130007529558
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- NII Book ID
- AN0024521X
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- ISSN
- 18836526
- 00379980
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- NDL BIB ID
- 029397764
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- Text Lang
- ja
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- Data Source
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- JaLC
- NDL
- Crossref
- CiNii Articles
- KAKEN
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- Abstract License Flag
- Disallowed