School of Chemistry, Raymond and Beverly Sackler Faculty of Exact Sciences, Tel Aviv University, Tel Aviv 69978, Israel.
Chem Commun (Camb). 2022 Nov 1;58(87):12176-12179. doi: 10.1039/d2cc04359a.
In this work the first examples of C-N bond activation by insertion into a geometrically constrained P-centre are shown. The mechanisms of these activation processes leading to new P species were studied both experimentally and computationally. Interestingly, in the case of insertion of the P-centre into an N-C(O)H bond, an unstable phosphoranyl-formaldehyde intermediate is probably formed, which undergoes decarbonylation in the presence of a catalytic amount of HCl producing a hydrophosphorane.
在这项工作中，首次展示了通过插入几何受限的 P 中心实现 C-N 键活化的实例。通过实验和计算研究了这些导致新 P 物种形成的活化过程的机制。有趣的是，在 P 中心插入 N-C(O)H 键的情况下，可能形成不稳定的膦醛亚甲基中间体，在催化量的 HCl 存在下发生脱羰反应，生成氢膦烷。
