Abstract
The complete catalytic reaction course for the organolanthanide-assisted intramolecular hydroamination/cyclization (IHC) of 4,5-heptadien-1-ylamine by a prototypical [(eta(5)-Me5C5)2LuCH(SiMe3)2] precatalyst has been critically scrutinized by employing a reliable DFT method. A computationally verified mechanistic scenario for the IHC of 1,3-disubstituted aminoallene substrates has been proposed that is consistent with the empirical rate law determined by experiment and accounts for crucial experimental observations. It involves kinetically rapid substrate association and dissociation equilibria, facile and reversible intramolecular allenic C=C insertion into the Ln-N bond, and turnover-limiting protonation of the azacycle's tether functionality, with the amine-amidoallene-Ln adduct complex representing the catalyst's resting state. This mechanistic scenario bears resemblance to the mechanism that has been recently proposed in a computational exploration of aminodiene IHC. The unique features of the IHC of the two substrate classes are discussed. Furthermore, the thermodynamic and kinetic factors that control the regio- and stereoselectivity of aminoallene IHC have been elucidated. These achievements have provided a deeper insight into the catalytic structure-reactivity relationships in organolanthanide-assisted cyclohydroamination of unsaturated C-C functionalities.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
