Kou Kevin G M, Le Diane N, Dong Vy M
Department of Chemistry, University of California , Irvine, California 92697, United States.
J Am Chem Soc. 2014 Jul 2;136(26):9471-6. doi: 10.1021/ja504296x. Epub 2014 Jun 17.
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）催化下，α-酮酰胺与脂肪醛发生分子间氢酰化反应。一种新设计的Josiphos配体能够以高原子经济性和对映选择性得到α-酰氧基酰胺。基于机理和动力学研究，我们提出了一条途径，其中铑在活化醛以进行交叉偶联中起双重作用。提供了一个立体化学模型来解释所观察到的对映诱导方向。
