Publication 3 of year 2021

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  1. Regiodivergent synthesis of pyrazino-indolines vs. triazocines via α-imino carbenes addition to imidazolidines
    Guarnieri-Ibáñez, A.; de Aguirre Fondevila, A.; Besnard, C.; Poblador Bahamonde, A. I.; Lacour, J.
    Chem. Sci. 2021, 12, 1479-1485

Hexahydropyrazinoindoles were prepared in a single step from N-sulfonyl triazoles and imidazolidines. Under dirhodium catalysis, α-imino carbenes were generated and formed nitrogen ylide intermediates that, after subsequent aminal opening, afforded the pyrazinoindoles predominantly via formal [1,2]-Stevens and tandem Friedel-Crafts cyclizations. Of mechanistic importance, a regiodivergent reactivity was engineered through the use of a specific unsymmetrically substituted imidazolidine that promoted the exclusive formation of 8-membered ring 1,3,6-triazocines. Based on DFT calculations, an original Curtin-Hammett-like situation was demonstrated for the mechanism. Further derivatizations led to functionalized tetrahydropyrazinoindoles in high yields.

For a highlight in the Swiss Science Concentrates of CHIMIA, see: https://doi.org/10.2533/chimia.2021.208

DOI: 10.1039/D0SC05725H 

open archive unige:148588