Ligand-Controlled Chemoselective C(acyl)-O Bond vs C(aryl)-C Bond Activation of Aromatic Esters in Nickel Catalyzed C(sp2)-C(sp3) Cross-Couplings.

摘要: A ligand-controlled and site-selective nickel catalyzed Suzuki–Miyaura cross-coupling reaction with aromatic esters alkyl organoboron reagents as coupling partners was developed. This methodology provides a facile route for C(sp2)–C(sp3) bond formation in straightforward fashion by successful suppression of the undesired β-hydride elimination process. By simply switching phosphorus ligand, ester substrates are converted into alkylated arenes ketone products, respectively. The utility this newly developed protocol demonstrated its wide substrate scope, broad functional group tolerance application synthesis key intermediates bioactive compounds. DFT studies on oxidative addition step helped rationalizing intriguing chemoselectivity: whereas complexes bidentate ligands favor C(aryl)–C cleavage leading to product via decarbonylative process, ...