The detailed mechanisms of Ni-catalyzed reductive arylalkylation of unactivated alkenes with aryl bromides to synthesize benzene-fused 5- and 6- cyclic compounds were systematically investigated by DFT calculations. Our finding reveals that, under the catalysis of a Ni/biOx system with Zn as a reductant, bromobenzene containing a terminal olefin unit preferentially undergoes traditional Heck cyclization and cross-coupling reactions, favoring the formation of 5- cyclization products. In contrast, when Zn is absent, Ni-alkyl species play a pivotal role, facilitating a rare 1,2-aryl migration followed by H-atom abstration, which selectively yields 6- cyclization products.
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Nickel-catalyzed reductive arylalkylation of alkenes: 5- cyclization 6- cyclization 1,2-aryl migration to 6- product.
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