Nickel-catalyzed reductive arylalkylation of alkenes: 5- exo cyclization vs. 6- endo cyclization vs. 1,2-aryl migration to 6- endo product

The detailed mechanisms of Ni-catalyzed reductive arylalkylation of unactivated alkenes with aryl bromides to synthesize benzene-fused 5- exo and 6- endo cyclic compounds were systematically investigated by DFT calculations. Our finding reveals that, under the catalysis of a Ni/biOx system with Zn a...

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Published inDalton transactions : an international journal of inorganic chemistry Vol. 54; no. 13; pp. 5419 - 5424
Main Authors Du, Yuxin, Wu, Hongli, Yang, Miao, She, Yuanbin, Yang, Yun-Fang
Format Journal Article
LanguageEnglish
Published England Royal Society of Chemistry 25.03.2025
Subjects
Alkenes
Aromatic compounds
Benzene
Bromides
Chemical reactions
Cross coupling
Cyclic compounds
Reducing agents
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Summary:The detailed mechanisms of Ni-catalyzed reductive arylalkylation of unactivated alkenes with aryl bromides to synthesize benzene-fused 5- exo and 6- endo 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- exo cyclization products. In contrast, when Zn is absent, Ni III -alkyl species play a pivotal role, facilitating a rare 1,2-aryl migration followed by H-atom abstration, which selectively yields 6- endo cyclization products.
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ISSN:1477-9226
1477-9234
1477-9234
DOI:10.1039/D5DT00094G