Synthesis of Tetra-ortho-Substituted Biaryls Using Aryltriolborates

Abstract

Tetra-ortho-substituted biaryls were synthesized by cross-coupling between 2,6-disubstituted bromoarenes and aryltriolborates possessing substituents at ortho carbon. The use of a copper(I) halide such as CuCl (20 mol%) with a palladium catalyst was found to be highly effective to give such sterically hindered biaryls in good yields.

cross-coupling - palladium catalyst - aryltriolborates - tetra-ortho-substituted biaryls

References and Notes

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22

General Procedure for the Synthesis of ortho -Substituted Biaryls
The aryl bromide (0.5 mmol), aryl triolborate (0.75 mmol), Pd(OAc)₂ (5 mol%), BIPHEP (5.5 mol%), and CuCl (0.1 mmol) were placed in a flash under nitrogen atmosphere. Anhyd DMF (5 mL) was added. The mixture was stirred at 80 ˚C for 14 h. After cooling to r.t., the crude mixture was filtered through a plug of Celite and washed with Et₂O. The filtrate was then concentrated in vacuo to afford the crude product, which was further purified by chromatography on silica gel with hexanes-EtOAc (99:1 to 10:1).

23 Tyrrell E. Brookes P. Synthesis  2003,  469