A Zinc Catalyzed C(sp3 )-C(sp2 ) Suzuki-Miyaura Cross-Coupling Reaction Mediated by Aryl-Zincates

Chemistry. 2017 Nov 13;23(63):15889-15893. doi: 10.1002/chem.201704170. Epub 2017 Oct 19.

Abstract

The Suzuki-Miyaura (SM) reaction is one of the most important methods for C-C bond formation in chemical synthesis. In this communication, we show for the first time that the low toxicity, inexpensive element zinc is able to catalyze SM reactions. The cross-coupling of benzyl bromides with aryl borates is catalyzed by ZnBr2 , in a process that is free from added ligand, and is compatible with a range of functionalized benzyl bromides and arylboronic acid pinacol esters. Initial mechanistic investigations indicate that the selective in situ formation of triaryl zincates is crucial to promote selective cross-coupling reactivity, which is facilitated by employing an arylborate of optimal nucleophilicity.

Keywords: alkylation; boron; cross-coupling; transmetallation; zincate.