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Stable Ambiphilic Bis(N-Heterocyclic Imino)-Substituted Terminal Olefin and Its Diazoolefin Derivative Exhibits
Bindusagar Das1, Dhananjay1, Aryan Chauhan1
1Department of Chemistry, Indian Institute of Technology Delhi, New Delhi, India.
Abstract:
In this article, we report a novel bis(N-heterocyclic imino) terminal olefin, [{(CAAC)N}2C═CH2] [CAAC = cyclic (alkyl)(amino)carbene], which exhibits reactivity distinct from traditional N-heterocyclic olefins. The use of the (CAAC)-derived ambiphilic N-heterocyclic imino fragment {(CAAC)N‒} was crucial in imparting the unique properties of [{(CAAC)N}2C═CH2]. The imino groups act as strong electron donors, rendering the terminal olefin polar through π-delocalization, whereas the carbenic carbon of CAAC introduces an electrophilic site into the imino substituent. This combination results in an inherently ambiphilic olefin that displays unusual reactivity. Specifically, the reaction of [{(CAAC)N}2C═CH2] with tosyl azide, under varying stoichiometric conditions, furnished four distinct nitrogen-rich compounds, including two unprecedented nitrogen-containing heterocycles. Quantum-chemical calculations were carried out to elucidate the bonding features of the ambiphilic bis-imino terminal olefin as well as the newly formed heterocycles.
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