3 years ago

Intramolecular Hydroamination by a Primary Amine of an Unactivated Alkene on Gold Nanoclusters: A DFT Study

Intramolecular Hydroamination by a Primary Amine of an Unactivated Alkene on Gold Nanoclusters: A DFT Study
Masahiro Ehara, Hidehiro Sakurai, Karan Bobuatong
Density functional theory calculations have been used to investigate the mechanism of intramolecular hydroamination of unactivated alkenes by using primary amines on gold nanoclusters (NCs) under aerobic conditions. By examining the activation modes in the cyclization process, the olefin activation mechanism was calculated to be the most energetically feasible of the three possible pathways. The amine activation pathway suffered from a high activation barrier, which means that this pathway is unlikely to take place on gold NCs. The catalytic cycle comprises five elementary steps: (1) adsorption of O2 on Au NCs results in superoxo-like species and provides Lewis acidic sites that allow the nucleophilic substrate, 2,2-diphenyl-4-penten-1-amine, to be adsorbed effectively; (2) intramolecular cyclization (C−N bond formation) takes place on the Au NCs through anti-addition of the amino group; (3) hydroperoxy moiety formation by hydrogen transfer from the cyclic intermediate to superoxo-like species; (4) the formation of hydrogen peroxide and (5) product involves hydrogen transfer from a hydrated formic acid. Natural bond orbital analysis of the transition states that arise during C−N bond formation reveals that anti-addition of the substrate is preferred over the syn-addition mechanism. A possible side reaction, the formation of 2-methylene-4,4-diphenylpyrrolidine through β-hydrogen elimination, is also discussed. Hydroamination mechanism: Density functional theory calculations have been used to investigate the mechanism of intramolecular hydroamination of unactivated alkenes by using primary amines on gold nanoclusters under aerobic conditions. The olefin activation mechanism was calculated to be the most energetically feasible of the three possible pathways, whereas the amine activation pathway suffered from a high activation barrier.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/cctc.201700839

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