The first example of organocatalytic aziridination reaction of α-substituted-α,β-unsaturated ketones was presented. The reaction was found to be highly enantio- and diastereoselective, yielding N-tosylated aziridines. Low temperature NMR spectra allowed for the determination of the N-inversion barrier, that was found to be quite lower with respect to unsubstituted aziridines. A thorough conformational analysis supported by low temperature NMR data allowed for the determination of the absolute configuration of the main stereoisomer by means of TD-DFT simulation of the ECD spectra
Bencivenni, G., Righi, P., Lunazzi, L., Ranieri, S., Mancinelli, M., Mazzanti, A. (2015). Enantioselective Preparation, Conformational Analysis and Absolute Configuration of Highly Substituted Aziridines. CHIRALITY, 27(12), 875-887 [10.1002/chir.22522].
Enantioselective Preparation, Conformational Analysis and Absolute Configuration of Highly Substituted Aziridines
BENCIVENNI, GIORGIO;RIGHI, PAOLO;LUNAZZI, LODOVICO;RANIERI, SILVIA;MANCINELLI, MICHELE;MAZZANTI, ANDREA
2015
Abstract
The first example of organocatalytic aziridination reaction of α-substituted-α,β-unsaturated ketones was presented. The reaction was found to be highly enantio- and diastereoselective, yielding N-tosylated aziridines. Low temperature NMR spectra allowed for the determination of the N-inversion barrier, that was found to be quite lower with respect to unsubstituted aziridines. A thorough conformational analysis supported by low temperature NMR data allowed for the determination of the absolute configuration of the main stereoisomer by means of TD-DFT simulation of the ECD spectraI documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
