Nature Commun. 2015, 6, 7508. DOI: 10.1038/ncomms8508

We have developed a user-friendly nickel-based catalytic system (Ni(OAc)2/P(n-Bu)3) for the decarbonylative organoboron cross-coupling using esters as coupling partners. In this report, we also described (1) the elucidation of key mechanistic features of this newly developed reaction by comprehensive theoretical calculation, (2) the broad scope with regard to both coupling partners (esters and boron), (3) successful aliphatic cross-coupling, (4) a gram-scale cross-coupling, (5) one-pot cross-coupling protocol starting directly from carboxylic acids, (6) application to complex molecular settings and (7) exceptionally high molecular recognition ability of Ni(OAc)2/P(n-Bu)3catalyst that allows unconventional orthogonal cross-coupling. Overall, the new ‘ester’ Suzuki–Miyaura coupling described herein not only is useful as an alternative to the standard halide-based cross-coupling, but also allows strategic and unconventional utilization of ubiquitous ester functionalities in chemical synthesis.