Suzuki-Miyaura Cross-Coupling of Aryl Fluorosulfonates Mediated by Air- and Moisture-stable [Pd(NHC)(μ-Cl)Cl]2 Precatalysts: Broad Platform for C-O Cross-Coupling of Stable Phenolic Electrophiles

A highly efficient protocol for the Suzuki-Miyaura cross-coupling of aryl fluorosulfonates by selective -OF cleavage using well-defined, air-and moisture-stable NHC-Pd(II) chloro dimers is presented. The reaction proceeds in excellent yields and with broad functional group tolerance using 0.10-0.20 mol % of [Pd] in the presence of mild K3PO4 base under aqueous conditions. A variety of sensitive functional groups are tolerated in this operationally trivial protocol for C-O bond activation. Selectivity studies and gram scale cross-coupling are presented. The method advances well-defined and highly reactive Pd(II)-NHCs to the cross coupling of readily available, orthogonal, and bench-stable fluorosulfonates as aryl halide surrogates.

Automated summary

A highly efficient protocol for the Suzuki-Miyaura cross-coupling of aryl fluorosulfonates using well-defined, air-and moisture-stable NHC-Pd(II) chloro dimers is presented. The reaction proceeds in excellent yields and with broad functional group tolerance using a very low loading of [Pd] in the presence of mild K3PO4 base under aqueous conditions. This operationally trivial protocol allows for the activation of C-O bond and is tolerant to various sensitive functional groups.