Control of Axial Chirality through NiH-Catalyzed Atroposelective Hydrofunctionalization of Alkynes

Catalytic asymmetric hydrofunctionalization of alkenes is a well-established method with which to construct complex C(sp3)-enriched molecules with central chirality. In contrast, the use of catalytic asymmetric hydrofunctionalization of abundant alkyne substrates to produce valuable multisubstituted alkenes with axial chirality remains largely unexplored. Here, we report a general procedure of this type catalyzed by abundant Ni(II) salts and employing a structurally simple chiral PyrOx ligand. A wide variety of structurally diverse atropisomeric chiral styrenes have been obtained from hydroarylation of alkynes with high efficiency, complete Z -selectivity, and excellent enantioselectivity.

Automated summary

Catalytic asymmetric hydrofunctionalization of alkenes is a well-established method for constructing complex C(sp3)-enriched molecules with central chirality. However, the use of this method for producing valuable multisubstituted alkenes with axial chirality from abundant alkyne substrates remains largely unexplored. In this study, a general procedure for catalytic asymmetric hydrofunctionalization of alkynes using abundant Ni(II) salts and a structurally simple chiral PyrOx ligand was developed. The reaction exhibited high efficiency, complete Z-selectivity, and excellent enantioselectivity, leading to the synthesis of diverse atropisomeric chiral styrenes.