Nickel-catalyzed reductive coupling of olefins represents an appealing strategy to access highly substituted molecules from a ubiquitous functional group. While recent advances have been made in this field, challenges associated with substrate scope and conditions infeasible for practical application must be addressed, and enantioselective intermolecular dicarbofunctionalization of alkenes has not yet been achieved. Asymmetric difunctionalization of olefins with readily available aryl bromide electrophiles without the use of air-sensitive organometallic reagents can provide a facile method for the preparation of complex products. In this work, we describe the development of a novel system utilizing a nickel catalyst with both <i>N</i>-oxyl and chiral bi(oxazoline) ligands and Zn powder as the reductant to achieve this transformation in good yield and with high enantioselectivity under mild reaction conditions. This reaction can be used to produce chiral targets with vicinal disubstituents that are otherwise challenging to access with existing strategies such as asymmetric hydrogenation, and can find broad application due to the availability of both alkenes and bromide electrophiles.

Enantioselective nickel-catalyzed reductive dicarbofunctionalization of olefins

256th National Meeting (2018)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.