The γ-functionalization of oxindoles bearing nonsymmetric 3-alkylidene groups via vinylogous Michael-type addition to nitroolefins was realized. The suppression of the interconversion between the E and Z isomers of the starting oxindoles allowed a site-specific diastereoselective and enantioselective transformation. Specific experiments allowed us to establish the rate-determining step of the reaction and to advance a robust hypothesis for the exclusive formation of an s-cis enolate as the only reactive intermediate.
Di Iorio, N., Righi, P., Ranieri, S., Mazzanti, A., Margutta, R., Bencivenni, G. (2015). Vinylogous Reactivity of Oxindoles Bearing Nonsymmetric 3-Alkylidene Groups. JOURNAL OF ORGANIC CHEMISTRY, 80(14), 7158-7171 [10.1021/acs.joc.5b01022].
Vinylogous Reactivity of Oxindoles Bearing Nonsymmetric 3-Alkylidene Groups
DI IORIO, NICOLA;RIGHI, PAOLO;RANIERI, SILVIA;MAZZANTI, ANDREA;BENCIVENNI, GIORGIO
2015
Abstract
The γ-functionalization of oxindoles bearing nonsymmetric 3-alkylidene groups via vinylogous Michael-type addition to nitroolefins was realized. The suppression of the interconversion between the E and Z isomers of the starting oxindoles allowed a site-specific diastereoselective and enantioselective transformation. Specific experiments allowed us to establish the rate-determining step of the reaction and to advance a robust hypothesis for the exclusive formation of an s-cis enolate as the only reactive intermediate.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
