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)（Rh(I)）催化下，α-酮酰胺可与脂肪族醛发生分子间加氢酰化反应。新设计的乔希福斯配体（Josiphos）能够以高原子经济性和优异对映选择性合成α-酰氧基酰胺。基于机理与动力学研究，我们提出了一条反应路径，其中铑在活化醛底物以参与交叉偶联的过程中发挥双重作用。本文构建了立体化学模型，以合理阐释实验中观测到的对映诱导的手性选择性取向。