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Nickel-Catalyzed 1,2-Carboamination of Alkenyl Alcohols
preprintsubmitted on 12.03.2021, 01:33 and posted on 16.03.2021, 10:50 by Taeho Kang, Nana Kim, Peter Cheng, Hao Zhang, Klement Foo, Keary Engle
An alcohol-directed, nickel-catalyzed three-component umpolung carboamination of unactivated alkenes with aryl/alkenylboronic esters and electrophilic aminating reagents is reported. This transformation is enabled by specifically tailored O-(2,6-dimethoxybenzoyl)hydroxylamine electrophiles that suppress competitive processes, including undesired β-hydride elimination and transesterification between the alcohol substrate and electrophile. The reaction delivers the desired 1,2-carboaminated products with excellent regio- and diastereoselectivity and exhibits a broad scope of coupling partners and alkenes, including complex natural products. Various mechanistic experiments and analysis of the stereochemical outcome with a cyclic alkene substrate, as confirmed by X-ray crystallographic analysis, support alcohol-directed syn-insertion of an organonickel(I) species.