Liang Haosheng, Bi Siwei, Liu Yuxia, Tang Ya-Nan, Liu Congcong
College of Chemistry and Chemical Engineering, Qufu Normal University, Qufu 273165, P. R. China.
Org Biomol Chem. 2016 Mar 7;14(9):2637-44. doi: 10.1039/c5ob02568k.
The Au-catalyzed [2 + 2 + 2] cycloadditions of ynamides with two discrete nitriles were theoretically studied with the aid of DFT calculations. The reaction under consideration is found to start from binding of the catalyst with the ynamide rather than with the nitrile. The Au(i)-ynamide species can effectively induce dimerization of two nitrile molecules while the catalyst only cannot. The Au(i)-ynamide species () is revealed to be more reactive than the Au(i)-nitrile species. Also, the regioselectivity and the influence of EWG vs. EDG involved in the reaction were also rationalized.
借助密度泛函理论（DFT）计算，对金催化的炔酰胺与两种不同腈的[2 + 2 + 2]环加成反应进行了理论研究。研究发现，所考虑的反应从催化剂与炔酰胺而非腈的结合开始。金（I）-炔酰胺物种可有效诱导两个腈分子二聚，而仅催化剂则不能。结果表明，金（I）-炔酰胺物种比金（I）-腈物种更具反应活性。此外，还对反应中的区域选择性以及吸电子基团（EWG）与给电子基团（EDG）的影响进行了合理解释。
