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Issue 27, 2015
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Aluminium-catalysed intramolecular hydroamination of aminoalkenes: computational perusal of alternative pathways for aminoalkene activation

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Abstract

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 σ-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 σ-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[double bond, length as m-dash]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.

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

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Supplementary files

Article information


Submitted
11 Jan 2015
Accepted
16 Mar 2015
First published
24 Mar 2015

Dalton Trans., 2015,44, 12169-12179
Article type
Paper
Author version available

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

S. Tobisch, Dalton Trans., 2015, 44, 12169
DOI: 10.1039/C5DT00121H

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