BH/CHとBH/NHの触媒カスケード脱水クロスカップリング:カーボラノ-イソキノリノンの1ポットプロセス
Yik Ki Au1, Hairong Lyu1, Yangjian Quan1
1Department of Chemistry and State Key Laboratory of Synthetic Chemistry , The Chinese University of Hong Kong , Shatin , NT, Hong Kong , China.
Journal of the American Chemical Society
|July 16, 2019
まとめ
この研究は,新しいカルボラノ-イソキノリノンの誘導体の1ポット合成を示しています. このプロセスは,カスケード脱水性クロスカップリング反応によって,効率的に新しいボロン-炭素およびボロン-窒素結合を形成する.
科学分野:
- 有機金属化学
- 合成有機化学
- ボロン化学
背景:
- カーボランの誘導体は,材料科学と医薬品化学において有価である.
- 複雑なカルボラン構造への効率的な合成経路は非常に求められています.
- カスケード反応は原子経済と 簡潔な合成経路を提供します
研究 の 目的:
- カーボラノ・イソキノリノンの誘導体を合成するための新しいカスケード脱水型クロスカップリング反応を開発する.
- 一ポットプロセスにおける複数の結合 (B-H,C-H,N-H) の連続的な活性化を調査する.
- 誘導群と潜在的触媒種の役割を含む反応機構を明らかにする.
主な方法:
- カスケード脱水性クロスカップリングを用いた原理実証研究.
- カーボラニルカルボキシル酸とベンザミドの1ポット反応
- ケージB-H,アリルC-H,およびN-H結合の配列活性化
- 循環と脱炭素化のステップ
- 電気化学分析 (CV) と対照実験
- 中間物質の分離と特徴付けとデュテリウムのラベル付け
主要な成果:
- 以前は入手不可能だったカルボラノ・イソキノリノンの産物の 容易な合成
- 新しいボロン-炭素 (B-C) とボロン-窒素 (B-N) 結合の効率的な構築
- 特定の条件下でB-Nに対する選択的なB-Cクロスカップリングの実証.
- カーボキシル酸を主要指向グループとして特定し,in situデカルボキシル化により除去する.
- 高価イリジウム (Ir(V)) 種とイリジウム-ニトロンの中間物質が関与していることを示唆する証拠.
結論:
- カーボラノ・イソキノリノンの誘導体を合成するための新しい効率的な"ポット"方法が確立されています.
- 反応は,選択的なB-C結合形成の可能性のある,連続的なB-H/C-HとB-H/N-Hクロスカップリングによって進行する.
- カーボキシル酸グループは,最初のB-C結合を指示する上で重要な役割を果たします.
- 機械的な洞察は,B-H/N-H脱水結合のための新しいIr-nitrene媒介アミネーション経路を指しています.
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