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三足四歯リガンドを持つ八面体複合体におけるキラリティの源としての金属
María Carmona1, Ricardo Rodríguez1, Vincenzo Passarelli1,2
1Departamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), CSIC - Universidad de Zaragoza , Pedro Cerbuna 12, 50009 Zaragoza, Spain.
Journal of the American Chemical Society
|January 6, 2018
まとめ
三脚リガンドを持つキラル金属複合体は,制御された絶対的構成を達成する. これらのエナチオピュアロジウム複合体は,高い選択性を持つダイエルス-アルダー反応をエナチオ選択的に触媒化する.
科学分野:
- 有機金属化学
- 非対称な触媒
- 協調化学
背景:
- キラル・アット・メタル複合体の絶対的構成を制御することは,合成化学における重要な課題である.
- 三脚四歯連鎖は,金属中心の周りのステレオ化学的制御を達成するための有望な支架を提供します.
研究 の 目的:
- キラル・アット・メタル・コンプレックスにおける絶対的な構成を効率的に制御する方法を開発する.
- 三脚の四歯状リガンドを用いて,エナンチオプアロジウム複合体を合成する.
- ダイエルス・アルダー反応におけるこれらの複合体のエナンチオセレクティブの触媒活性を調べる.
主な方法:
- (S) -α-フェニルグリシンを使用したラセミックロジウム複合体の光学解像度.
- 一般式[Rh(κ4C,N,N',P-L) A(Solv) ][SbF6]nのエナンチオプアロジウム複合体の合成
- メタクロレインとサイクロペンタディエン (HCp) の間のエナンチオセレクティブ・ディエルス-アルダー反応触媒.
- 核磁共振 (NMR) スペクトロスコーピーと密度関数理論 (DFT) 研究を用いた特徴付け.
主要な成果:
- チラル・アット・メタル複合体の絶対的構成の効率的な制御は,三足の四歯状リガンドLを用いて達成された.
- 光学的な解像度は,ダイエルス-アルダー反応を触媒にできるエナチオピュアロジウム複合体を生成した.
- メタクロレインとHCpの間のディエルス-アルダー反応で,最大99/ 1のエナティオメール比が得られた.
- NMRとDFTの研究では,活性種,エナント選択性の起源,およびメカニズム的な詳細が明らかにされました.
結論:
- 三脚の四歯状リガンドLは,キラル・アット・メタル複合体の絶対的構成を制御するのに有効です.
- 合成されたエナチオピュアロジウム複合体は,ダイエルス-アルダー反応の非常に効果的なエナチオ選択的触媒である.
- 触媒過程とエナチオ選択性の起源に関する詳細なメカニズム的な洞察が得られた.
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