A General, Efficient, and Functional-Group-Tolerant Catalyst System for the Palladium-Catalyzed Thioetherification of Aryl Bromides and Iodides

Reaction Scheme

Abstract

On the basis of mechanism-driven reaction design, a Pd-catalyzed nucleophilic fluorination of aryl bromides and iodides has been developed. The method exhibits a broad substrate scope, especially with respect to nitrogen-containing heteroaryl bromides, and proceeds with minimal formation of the corresponding reduction products. A facilitated ligand modification process was shown to be critical to the success of the reaction.

Substrates

Procedure

The reactions were set up in a nitrogen-filled glovebox. A reaction tube was charged with AgF (254 mg, 2.00 mmol, 2.00 equiv.), KF (29.1 mg, 0.500 mmol, 0.500 equiv.), 2, reaction solvent (10 mL), and aryl halide (1.00 mmol, 1.00 equiv.), in that order. The tube was sealed with a Teflon cap, removed from the glovebox, and heated to the designated temperature in a pre-heated oil bath. The reaction mixture was vigorously stirred for 14 h. The reaction mixture was cooled to room temperature and filtered through a pad of Celite, eluting with diethyl ether. After concentration, the crude product was purified by silica gel chromatography.

Products

Materials

     
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