化学
对映选择合成
重氮
钴
催化作用
卡宾
亲核细胞
氢键
药物化学
插入反应
有机化学
分子
作者
Wei Yang,Maoping Pu,Xiaobin Lin,Min Chen,Yanji Song,Xiaohua Liu,Yun‐Dong Wu,Xiaoming Feng
摘要
Vinylcarbene insertion into the nitrogen–hydrogen (N–H) bond of amines allows direct access to α,β-unsaturated γ-amino acid derivatives, meeting a marked challenge in the control of regio- and enantioselectivities. Here, we report a highly γ-selective and enantioselective insertion into N–H bonds of aliphatic or aromatic secondary amines with vinyl substituted α-diazo pyrazoleamides using a high-spin chiral N,N′-dioxide/cobalt(II) complex catalyst. The method affords a wide variety of valuable optically active Z- and E-type vinyl γ-amino amides. Calculation reveals a spin state change from the quartet cobalt(II) complex to a doublet Co(II)-carbene species for facile Z-selective and enantioselective nucleophilic addition.
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