Solvent-Switchable Remote C-H Activation via 1,4-Palladium Migration Enables Site-Selective C-P Bond Formation: A
Ifenna I Mbaezue1, Shi-Guang Li1, Angula C S Reddy1
1Department of Chemistry, McGill University. 801 Sherbrooke St. West, Montréal, Québec H3A 0B8, Canada.
Abstract:
Solvent-switchable and site-selective phosphorylation of imidazoles at the C2 or C5 position of the imidazole ring was achieved via 1,4-palladium migration. P-Chiral tert-butyl(aryl)phosphine oxides were cross-coupled to 1-(2-bromophenyl)-1H-imidazoles with high enantiospecificity, thereby leading to a novel class of chiral imidazole-based phosphine oxides. As proof of concept, reduction of an analogue yielded the corresponding P-chiral 2-phosphinyl imidazole ligand, which was shown to induce high enantioselectivity in the formation of axially chiral molecules synthesized via Pd-catalyzed Suzuki-Miyaura cross-coupling.
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