The present work is aimed at shedding light on the origin of the stereoselectivity observed in the reactions of chiral heterosubstituted organolithiums, generated by lithiation of alkylideneaziridines. Factors such as the nitrogen inversion barrier, the stereochemistry at the nitrogen atom, the substitution pattern of the alkylideneaziridines, and the reaction conditions are taken into consideration. The interplay between nitrogen stereodynamics and complexation phenomena seems to be crucial in determining the stereo chemical outcome of the lithiation/trapping sequence. The findings were rationalized by a synergistic use of NMR experiments, run on the lithiated intermediates, alongside computational data. It has been demonstrated that, in such systems, the stereochemistry-determining step is the deprotonation reaction, and a model based on a deprotonative dynamic resolution has been proposed. Such findings could find application in dynamic systems than aziridines. OI Degennaro, Leonardo/0000-0002-2187-9419

Nitrogen Stereodynamics and Complexation Phenomena as Key Factors in the Deprotonative Dynamic Resolution of Alkylideneaziridines: A Spectroscopic and Computational Study / Degennaro, Leonardo; Pisano, Luisa; Parisi, Giovanna; Mansueto, Rosmara; Clarkson Guy, J.; Shipman, Michael; Luisi, Renzo. - In: JOURNAL OF ORGANIC CHEMISTRY. - ISSN 0022-3263. - 80:12(2015), pp. 6411-6418. [10.1021/acs.joc.5b00848]

Nitrogen Stereodynamics and Complexation Phenomena as Key Factors in the Deprotonative Dynamic Resolution of Alkylideneaziridines: A Spectroscopic and Computational Study

PISANO, Luisa;
2015-01-01

Abstract

The present work is aimed at shedding light on the origin of the stereoselectivity observed in the reactions of chiral heterosubstituted organolithiums, generated by lithiation of alkylideneaziridines. Factors such as the nitrogen inversion barrier, the stereochemistry at the nitrogen atom, the substitution pattern of the alkylideneaziridines, and the reaction conditions are taken into consideration. The interplay between nitrogen stereodynamics and complexation phenomena seems to be crucial in determining the stereo chemical outcome of the lithiation/trapping sequence. The findings were rationalized by a synergistic use of NMR experiments, run on the lithiated intermediates, alongside computational data. It has been demonstrated that, in such systems, the stereochemistry-determining step is the deprotonation reaction, and a model based on a deprotonative dynamic resolution has been proposed. Such findings could find application in dynamic systems than aziridines. OI Degennaro, Leonardo/0000-0002-2187-9419
2015
Nitrogen Stereodynamics and Complexation Phenomena as Key Factors in the Deprotonative Dynamic Resolution of Alkylideneaziridines: A Spectroscopic and Computational Study / Degennaro, Leonardo; Pisano, Luisa; Parisi, Giovanna; Mansueto, Rosmara; Clarkson Guy, J.; Shipman, Michael; Luisi, Renzo. - In: JOURNAL OF ORGANIC CHEMISTRY. - ISSN 0022-3263. - 80:12(2015), pp. 6411-6418. [10.1021/acs.joc.5b00848]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11388/59740
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