科研之友
微信
新浪微博
Facebook
分享链接
摘要
Metal-associated carbenes from diazo compounds promote many useful chemistry transformations in modern organic chemistry. However, compared to alpha-aryldiazoacetate-derived carbenes (ArDCs), the synthetic application of alpha-alkyldiazoacetate-derived carbenes (AlDCs) is greatly limited due to intramolecular alpha-H transfer (elimination) that results in alkenes as the main by-products. An intriguing aalkyldiazoacetate- involved three-component reaction has been developed following DFT calculation inspiration to provide beta-hydroxyl alpha-alkyl-alpha-amino acid derivatives in good yields. The intramolecular alpha-H shift of an alpha-alkyldiazoacetate-derived carbene was successfully suppressed by the association of a Rh(I) complex to form the corresponding active ammonium ylide, which was trapped before the fast 1,2-H transfer process. A Rh(I)-chiral diene complex was identified as an effective catalyst to give an asymmetric version of the reaction with good enantioselectivity. This reaction provides insight into extending the efficient transformation of alpha-alkyldiazoacetate-derived carbenes and their synthetic application.
