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

preprint
submitted on 08.04.2021, 16:52 and posted on 09.04.2021, 10:46 by Sii Hong Lau, Meredith Borden, Talia Steiman, Lucy Wang, Marvin Parasram, Abigail Doyle
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. Mechanistic studies were conducted, lending support to the hypothesis that 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.

Funding

NIGMS R35 GM126986

History

Email Address of Submitting Author

agdoyle@princeton.edu

Institution

Princeton University

Country

United States

ORCID For Submitting Author

0000-0002-6641-0833

Declaration of Conflict of Interest

no conflict of interest

Version Notes

Manuscript Version 1

Exports