Aromatic C–H Thioalkylphosphinylation of [2.2]Paracyclophanes via Sulfonium Salts

作者：Mingrui Li, Juan Ma, Liandi Wang, Kaikai Wu, Yong‐Gui Zhou, Zhengkun Yu · 发表于：The Journal of Organic Chemistry · 年份：2025 · DOI：10.1021/acs.joc.5c01085 · 被引用次数：5 · 研究领域：Organophosphorus compounds synthesis、Asymmetric Hydrogenation and Catalysis、Chemical Synthesis and Analysis

Base-enabled aromatic C–H functionalization of [2.2]paracyclophanes was achieved by thioalkylphosphinylation via sulfonium salts. Cross-coupling between [2.2]paracyclophane tetrahydro-1 H -thiophen-1-ium trifluoromethanesulfonates and secondary phosphine oxides afforded thioalkylphosphinylated [2.2]paracyclophane derivatives through selective C(sp 3 )–S bond cleavage of the arylsulfonium salts under mild conditions. The protocol features broad substrate scopes, good functional group tolerance from readily available reagents, and decent efficiency in up to 96% yields. The practicability of this method was demonstrated by scale-up preparation of the target products and their transformations to potential P,S-ligands for Suzuki and Sonogashira cross-coupling reactions.