C(sp ² )–C(sp ² ) and C(sp ² )–C(sp ³ ) nickel-catalyzed Kumada–Corriu and Buchwald–Hartwig cross-coupling of aryl sulfamates enabled by sterically-demanding, electron-rich IPr* ^OMe <i>N</i> -het

Nickel-catalyzed cross-coupling reactions are among the most powerful tools in organic synthesis owing to the low cost, natural abundance and high activity of versatile nickel catalysts. However, there is a scarcity of efficient Ni-catalyzed systems for the cross-coupling of bench-stable, readily accessible and orthogonal C-O electrophiles. Herein, we report the cross-coupling of aryl sulfamates enabled by sterically-demanding and electron-rich N-heterocyclic carbenes. The study identified sulfamates as the most reactive C-O electrophiles enabled by a combination of IPr*^OMe bearing sterically-demanding <i>ortho</i>-diphenyl wingtip substitution and NiF₂ exploiting the fluoride effect. The system enables efficient C(sp²)-C(sp²) and C(sp²)-C(sp³) cross-coupling avoiding hydrolysis, homocoupling and unselective C-O and S-N cleavages, providing a powerful platform for the orthogonal use of C-O electrophiles. The system is also applicable to Buchwald-Hartwig amination. The broad access to electron-rich, sterically-demanding N-heterocyclic carbenes combined with the high reactivity of aryl sulfamates furnishes a commanding avenue for the development of Ni-catalyzed processes in academic and industrial research.