Rh(I)-Catalyzed Intermolecular Hydroacylation: Enantioselective Cross-Coupling of Aldehydes and Ketoamides

Under Rh­(I) catalysis, α-keto­amides undergo inter­molecular hydro­acylation with aliphatic aldehydes. A newly designed Josiphos ligand enables access to α-acyl­oxyamides with high atom-economy and enantio­selectivity. On the basis of mechanistic and kinetic studies, we propose a pathway in which rhodium plays a dual role in activating the aldehyde for cross-coupling. A stereo­chemical model is provided to rationalize the sense of enantioinduction observed.在铑(I)催化条件下，α-酮酰胺可与脂肪族醛发生分子间氢酰化反应。本研究新设计的乔西福斯配体(Josiphos)可实现兼具高原子经济性与高对映选择性的α-酰氧基酰胺合成。基于机理与动力学研究，我们提出一条反应路径，其中铑发挥双重作用，可活化醛以参与交叉偶联。此外，本文构建了立体化学模型，用以合理解释所观测到的对映诱导方向。