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![[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
Published on: May 21, 2019
Ligand-Controlled Regioinduction in a PHOX-Ni Aryne Complex
Alexander Umanzor1, Nicholas A Garcia1, Courtney C Roberts1
1Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455, United States.
Abstract:
Phosphinooxazoline (PHOX) ligands have been used to control the regio- and enantioselectivity in a wide variety of metal-catalyzed reactions. Despite their widespread use, PHOX ligands have never been studied in metal-aryne complexes. Herein we report the first example of a PHOX-Ni aryne complex. As demonstrated in other systems, the differentiated P versus N donors and different steric environments of the unsymmetric ligand are able to induce regiocontrol. A 81:19 mixture of o-methoxy substituted aryne complexes is observed. Single-crystal X-ray crystallographic analysis, UV/vis spectroscopy, and cyclic voltammetry are used to gain further insight into the molecular and electronic structure of these complexes. Lastly, a methylation/deuteration sequence shows retention of the PHOX ligand-induced regiocontrol in the difunctionalized products and that the regiospecificity of these difunctionalizations is due to the trans influence of the P donor.
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