DOI: 10.1021/acs.orglett.6c04068 ISSN: 1523-7060
Photoinduced Charge-Transfer Complex-Mediated Decarboxylative Phosphoniumation
Hailong He, Jiajin Chen, Hongyao Wang, Wenlong He, Tao Zhou, Zihao Chen, Zhiyan Xue, Qilong Wu, Ziyi Xu, Shuyang Liu, Yunhe JinAbstract
Phosphonium salts are valuable intermediates in organic synthesis, but their preparation often requires harsh conditions and specific carbon precursors. Herein, we report a photoinduced decarboxylative phosphoniumation of redox-active esters (RAEs) for the direct synthesis of alkyl and benzyl phosphonium salts. A photoresponsive ternary charge-transfer complex (CTC) formed from NaI, tertiary phosphines, and RAEs enables the reaction under transition-metal- and external-photocatalyst-free conditions. The method tolerates diverse benzyl and aliphatic RAEs and tertiary phosphines, including commercial phosphine ligand frameworks, and enables the late-stage phosphoniumation of complex carboxylic-acid-derived substrates.