Pizarro Juan Diego, Schmidtke Inga L, Nova Ainara, Fructos Manuel R, Pérez Pedro J
Laboratorio de Catálisis Homogénea, Unidad Asociada al CSIC, CIQSO-Centro de Investigación en Química Sostenible and Departamento de Química, Universidad de Huelva, 21007 Huelva, Spain.
Department of Chemistry, Hylleraas Centre for Quantum Molecular Sciences and Centre for Materials Science and Nanotechnology, University of Oslo, N-0315 Oslo, Norway.
ACS Catal. 2022 Jun 17;12(12):6851-6856. doi: 10.1021/acscatal.2c01713. Epub 2022 May 25.
The complete regioselective incorporation of carbene units to nonactivated arene rings has been achieved employing gold(I) catalysts bearing alkoxydiaminophosphine ligands, with readily available, nonelaborated ethyl 2-phenyldiazoacetate as the carbene source. These results are in contrast with the scarce precedents which required highly elaborated diazo substrates. Density functional theory (DFT) calculations have revealed the important role of the R group in the C(R)COEt fragment, which dramatically affects the energy profile of this transformation.
利用带有烷氧基二氨基膦配体的金（I）催化剂，以易于获得、无需复杂合成的2-苯基重氮乙酸乙酯作为卡宾源，已实现卡宾单元向未活化芳烃环的完全区域选择性引入。这些结果与少数需要高度复杂重氮底物的先例形成对比。密度泛函理论（DFT）计算揭示了C（R）COEt片段中R基团的重要作用，它极大地影响了这种转化的能量分布。
