American Chemical Society
ol8b04135_si_001.pdf (21.98 MB)

aza-Wittig Reaction with Nitriles: How Carbonyl Function Switches from Reacting to Activating

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journal contribution
posted on 2019-02-07, 16:21 authored by Hamidulla B. Tukhtaev, Konstantin L. Ivanov, Stanislav I. Bezzubov, Dmitry A. Cheshkov, Mikhail Ya. Melnikov, Ekaterina M. Budynina
Transformations of α-EWG-substituted (electron-withdrawing group, EWG) γ-azidobutyronitriles proceeding via unusual aza-Wittig reactions between the phosphazene and nitrile functions and affording pyrrole-derived iminophosphazenes were developed. α-EWGs were found to control chemoselectivity and, depending on their nature, act as CN group activators (e.g., ester, amide, or nitrile) or competitors (e.g., ketone) in aza-Wittig reactions. To demonstrate the synthetic utility of the obtained iminophosphazenes as N,N-binucleophiles, their transformations into pyrrole-fused systems, pyrrolo­[1,2-a]­imidazoles and pyrrolo­[1,2-a]­[1,3]­diazepines, were carried out.