書誌事項
- タイトル別名
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- Synthesis and Unique Catalytic Reactivity of Metal Complexes with Chelate-Type Silyl Ligands Connected by Xanthene
- 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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<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>
収録刊行物
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- 有機合成化学協会誌
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有機合成化学協会誌 76 (12), 1301-1309, 2018-12-01
公益社団法人 有機合成化学協会
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詳細情報 詳細情報について
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- CRID
- 1390845713030079360
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- NII論文ID
- 130007529558
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- NII書誌ID
- AN0024521X
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- ISSN
- 18836526
- 00379980
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- NDL書誌ID
- 029397764
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- 本文言語コード
- ja
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- データソース種別
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- JaLC
- NDL
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- 使用不可