Base-Controlled One-Pot Chemoselective Suzuki–Miyaura Reactions for the Synthesis of Unsymmetrical Terphenyls

Abstract

We report a chemoselective Suzuki–Miyaura reaction protocol of using bromophenyl fluorosulfonate as building block for the preparation of unsymmetrical terphenyls. The chemoselective cross-coupling of bromophenyl fluorosulfonate and arylboronic acids can be achieved by controlling base species without using any ligands. Under this methodology, various of m- and p-unsymmetrical terphenyls were obtained in moderate to good yields.

Ruthenium‐Catalyzed Synthesis of Aryl and Alkenyl Halides from Fluorosulfonates

“…Since the formation of fluorosulfonates only requires a base and sulfuryl fluoride, that can be easily removed by flushing argon into the reaction mixture, this transformation is very suitable for one-pot processes. [38][39][40] We were able to easily convert 4nitrophenol into the corresponding aryl halide 2 h in 83 % yield by forming the fluorosulfonate in DMPU, removing the sulfuryl fluoride and adding the ruthenium catalyst and lithium bromide (Scheme 4). This traceless one-pot process, starting from the phenol, is more efficient than in two steps, for which the overall yield is 66 %.…”