Ni/Photoredox-Catalyzed Enantioselective Cross-Electrophile Coupling of Styrene Oxides with Aryl Iodides

A Ni/photoredox- catalyzed enantioselective reductive coupling of styrene oxides and aryl iodides is reported. This reaction affords access to enantioenriched 2,2-diarylalcohols from racemic epoxides via a stereoconvergent mechanism. Multivariate linear regression (MVLR) analysis with 29 bioxazoline (BiOx) and biimidazoline (BiIm) ligands revealed that enantioselectivity correlates with electronic properties of the ligands, with more electron-donating ligands affording higher ee's. Experimental and computational mechanistic studies were conducted, lending support to the hypothesis that reductive elimination is enantiodetermining and the electronic character of the ligands influences the enantioselectivity by altering the position of the transition state structure along the reaction coordinate. This study demonstrates the benefits of utilizing statistical modeling as a platform for mechanistic understanding and provides new insight into an emerging class of chiral ligands for stereoconvergent Ni and Ni/photoredox cross-coupling.

Automated summary

This study introduces a Ni/photoredox-catalyzed enantioselective reductive coupling of styrene oxides and aryl iodides, yielding enantioenriched 2,2-diarylalcohols. Analysis shows that enantioselectivity is correlated with the electronic properties of the ligands, with more electron-donating ligands leading to higher ee values. Experimental and computational studies support the hypothesis that reductive elimination is enantiodetermining and ligand electronic properties affect enantioselectivity by altering the position of the transition state structure.