Aluminium-catalysed intramolecular hydroamination of aminoalkenes: computational perusal of alternative pathways for aminoalkene activation

作者：Tobisch Sven^*

来源：Dalton Transactions, 2015, 44(27): 12169-12179.

DOI：10.1039/c5dt00121h

A comprehensive computational examination of alternatively plausible mechanistic pathways for the intramolecular hydroamination (HA) of aminoalkenes utilising a recently reported novel phenylene-diamine aluminium amido compound is presented. On the one hand, a proton-assisted concerted N-C/C-H bond-forming pathway to afford the cycloamine in a single step can be invoked, and, on the other, a stepwise sigma-insertive pathway that involves a relatively fast, reversible migratory olefin 1,2-insertion step linked to a less rapid, irreversible Al-C alkyl bond protonolysis. The present study, which employs a sophisticated and reliable computational methodology, supports the prevailing mechanism to be a stepwise s-insertive pathway. The predicted effective barrier for turnover-limiting aminolysis compares favourably with reported catalytic performance data. Non-competitive kinetic demands militates against the operation of the concerted proton-assisted pathway, which describes N-C bond-forming ring closure triggered by concomitant amino proton delivery at the C=C linkage evolving through a six-centre transition state structure. The valuable insights into mechanistic intricacies of aluminium-mediated intramolecular HA reported herein will help guide the rational design of group 13 metal-based HA catalysts.

• 出版日期2015