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Molybdenum-Catalyzed Asymmetric Hydrogenation of Fused Arenes and Heteroarenes
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2022-06-17 , DOI: 10.1021/jacs.2c02007 Peter Viereck 1 , Gabriele Hierlmeier 1 , Paolo Tosatti 2 , Tyler P Pabst 1 , Kurt Puentener 2 , Paul J Chirik 1
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2022-06-17 , DOI: 10.1021/jacs.2c02007 Peter Viereck 1 , Gabriele Hierlmeier 1 , Paolo Tosatti 2 , Tyler P Pabst 1 , Kurt Puentener 2 , Paul J Chirik 1
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The synthesis of enantioenriched molybdenum precatalysts for the asymmetric hydrogenation of substituted quinolines and naphthalenes is described. Three classes of pincer ligands with chiral substituents were evaluated as supporting ligands in the molybdenum-catalyzed hydrogenation reactions, where oxazoline imino(pyridine) chelates were identified as optimal. A series of 2,6-disubstituted quinolines was hydrogenated to enantioenriched decahydroquinolines with high diastereo- and enantioselectivities. For quinoline derivatives, selective hydrogenation of both the carbocycle and heterocycle was observed depending on the ring substitution. Spectroscopic and mechanistic studies established molybdenum η6-arene complexes as the catalyst resting state and that partial hydrogenation arises from dissociation of the substrate from the coordination sphere of molybdenum prior to complete reduction. A stereochemical model is proposed based on the relative energies of the respective coordination of the prochiral faces of the arene determined by steric interactions between the substrate and the chiral ligand, rather than through precoordination by a heteroatom.
中文翻译：
钼催化稠合芳烃和杂芳烃的不对称氢化
描述了用于取代喹啉和萘不对称氢化的对映富钼预催化剂的合成。三类具有手性取代基的钳形配体被评估为钼催化氢化反应中的支持配体，其中恶唑啉亚氨基（吡啶）螯合物被确定为最佳配体。一系列 2,6-二取代的喹啉被氢化成对映富集的十氢喹啉，具有高非对映选择性和对映选择性。对于喹啉衍生物，根据环取代观察到碳环和杂环的选择性氢化。光谱和机理研究确定钼 η 6-芳烃配合物作为催化剂的静止状态，部分氢化是由于底物在完全还原之前从钼的配位层解离而产生的。基于由底物和手性配体之间的空间相互作用确定的芳烃前手性面各自配位的相对能量，而不是通过杂原子的预配位，提出了立体化学模型。
更新日期：2022-06-17
中文翻译：
钼催化稠合芳烃和杂芳烃的不对称氢化
描述了用于取代喹啉和萘不对称氢化的对映富钼预催化剂的合成。三类具有手性取代基的钳形配体被评估为钼催化氢化反应中的支持配体，其中恶唑啉亚氨基（吡啶）螯合物被确定为最佳配体。一系列 2,6-二取代的喹啉被氢化成对映富集的十氢喹啉，具有高非对映选择性和对映选择性。对于喹啉衍生物，根据环取代观察到碳环和杂环的选择性氢化。光谱和机理研究确定钼 η 6-芳烃配合物作为催化剂的静止状态，部分氢化是由于底物在完全还原之前从钼的配位层解离而产生的。基于由底物和手性配体之间的空间相互作用确定的芳烃前手性面各自配位的相对能量，而不是通过杂原子的预配位，提出了立体化学模型。
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