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Nickel-Catalyzed Benzylation of Aryl Alkenes with Benzylamines via C–N Bond Activation
- Yu, Hui, Hu, Bin, Huang, Hanmin
- Journal of organic chemistry 2018 v.83 no.22 pp. 13922-13929
- Lewis acids, alkenes, benzylamines, benzylation, chemical bonding, chemical structure, cleavage (chemistry), iodine, nickel, organic chemistry, oxidants
- We have developed the first example of nickel-catalyzed Heck-type benzylation of aryl olefins with various benzylamines as benzyl electrophiles, and the benzylic C–N bond cleavage was efficiently promoted by the amine–I₂ charge transfer complex (CT complex). The combination of low-cost NiCl₂ and I₂ has been found to facilitate Heck reaction of tertiary benzylamines and alkenes into various benzyl-substituted alkenes in good to excellent yields. This unconventional Heck reaction is proposed to go through initially the formation of a benzylic radical via oxidative addition of the C–N bond with Ni(0), then capturing by aryl alkene via radical addition, followed by single-electron transfer redox and proton abstraction without oxidant and external base.