Trifluoromethylthiolation of aryl iodides and bromides enabled by a bench-stable and easy-to-recover dinuclear palladium(I) catalyst.
While palladium catalysis is ubiquitous in modern chemical research, the recovery of the active transition-metal complex under routine laboratory applications is frequently challenging. Described herein is the concept of alternative cross-coupling cycles with a more robust (air-, moisture-, and thermally-stable) dinuclear Pd(I) complex, thus avoiding the handling of sensitive Pd(0) species or ligands. Highly efficient C-SCF3 coupling of a range of aryl iodides and bromides was achieved, and the recovery of the Pd(I) complex was accomplished via simple open-atmosphere column chromatography. Kinetic and computational data support the feasibility of dinuclear Pd(I) catalysis. A novel SCF3-bridged Pd(I) dimer was isolated, characterized by X-ray crystallography, and verified to be a competent catalytic intermediate.
Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen (Germany) http://www.schoenebeck.oc.rwth-aachen.de/
Guoyin
G
Yin
Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen (Germany) http://www.schoenebeck.oc.rwth-aachen.de/
Indrek
I
Kalvet
Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen (Germany) http://www.schoenebeck.oc.rwth-aachen.de/. franziska.schoenebeck@rwth-aachen.de.
Franziska
F
Schoenebeck
cross-coupling; density functional theory calculations; palladium; reaction mechanisms; synthetic methods