Ailin Pan, Madeline E. Rotella, Yamiao Meng, Xun Tian, Shengzu Duan, Yonggang Jiang, Guogang Deng, Bart Limburg, Hongbin Zhang, Marisa C. Kozlowski, Patrick J. Walsh, Xiaodong Yang
deprotonation of N-centered radicals without the requirement of external strong bases, instead being facilitated by the benzoate anion generated during the reaction. This process enables the synthesis of α-amino phosphine oxides bearing various functional groups under mild conditions. The gram-scale synthesis demonstrates the scalability of the net 1,2-HAT rearrangement/radical-radical coupling reaction, which has been used in the preparation of an antitumor agent. Mechanistic investigations, including radical trapping experiments, Stern-Volmer fluorescence quenching experiments, cyclic voltammogram studies, cross-over experiments, KIE studies and DFT calculations support a net 1,2-HAT pathway.