Department of Chemistry, Wroclaw University , F. Joliot-Curie 14, Wroclaw 50-383, Poland.
Department of Chemistry, Rutgers University , 73 Warren Street, Newark, New Jersey 07102, United States.
J Org Chem. 2017 Jun 16;82(12):6373-6378. doi: 10.1021/acs.joc.7b00971. Epub 2017 Jun 7.
Transition-metal-catalyzed activation of amide N-C(O) bonds proceeds via selective metal insertion into the carbon-nitrogen amide bond. Herein, we demonstrate that N-acylanilines (anilides), the first class of planar amides that have been shown to undergo selective amide N-C cross-coupling reactions, feature a significantly decreased barrier to rotation around the amide N-C(O) bond. Most significantly, we demonstrate that amide n → π* resonance in simple anilides can be varied by as much as 10 kcal/mol. The data have important implications for the design of N-C(O) amide cross-coupling reactions and control of the molecular conformation of anilides by resonance effects.
过渡金属催化的酰胺 N-C(O) 键的活化是通过选择性的金属插入到碳-氮酰胺键中进行的。在此，我们证明 N-酰基苯胺（酰胺），即第一类已被证明能进行选择性酰胺 N-C 交叉偶联反应的平面酰胺，其酰胺 N-C(O) 键的旋转障碍明显降低。最重要的是，我们证明了简单的酰基苯胺中的酰胺 n → π* 共振可以变化高达 10 kcal/mol。这些数据对 N-C(O) 酰胺交叉偶联反应的设计以及通过共振效应控制酰基苯胺的分子构象具有重要意义。
