化学
卡宾
对映选择合成
胍
位阻效应
有机催化
双功能
酰胺
氢键
催化作用
组合化学
药物化学
立体化学
光化学
有机化学
分子
作者
Shiyang Li,Cefei Zhang,Guihua Pan,Liangkun Yang,Zhishan Su,Xiaoming Feng,Xiaohua Liu
标识
DOI:10.1021/acscatal.3c00192
摘要
A visible-light-induced enantioselective free carbene transfer reaction of α-diazoesters with 1,3-diketones is established by utilizing a chiral bifunctional guanidine-amide organocatalyst. Selective insertion of free carbene into the C–C or C–H bonds of 1,3-diketone could be achieved with α-diazoesters bearing different steric hindrances. The transformations enable the preparation of a series of 1,4-diketones with a quaternary carbon chiral center or chiral 2-substituted-1,3-diketones in good enantioselectivities. On the basis of the control experiments and DFT calculation, a stepwise triplet free carbene coupling pathway is suggested. A possible reaction mechanism is proposed to explain the origin of high enantioselectivities via hydrogen-bonds and electrostatic interactions of the catalyst.
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