An efficient organocatalytic stereoselective reduction of -trifluoromethyl-substituted nitroalkenes, mediated by 3,5-dicarboxylic ester-dihydropyridines (Hantzsch ester type), has been successfully developed. A multifunctional thiourea-based (S)-valine derivative was found to be the catalyst of choice, promoting the reaction in up to 97%ee. The methodology has been applied to a wide variety of substrates, leading to the formation of differently substituted precursors of enantiomerically enriched -trifluoromethyl amines. The mechanism of the reaction and the mode of action of the metal-free catalytic species were computationally investigated; on the basis of DFT transition-state (TS) analysis, a model of stereoselection was also proposed.
Enantioselective organocatalytic reduction of beta-trifluoromethyl nitroalkenes: an efficient strategy for the synthesis of chiral beta-trifluoromethyl amines / E. Massolo, M. Benaglia, M. Orlandi, S. Rossi, G. Celentano. - In: CHEMISTRY-A EUROPEAN JOURNAL. - ISSN 0947-6539. - 21:9(2015 Feb 23), pp. 3589-3595.
|Titolo:||Enantioselective organocatalytic reduction of beta-trifluoromethyl nitroalkenes: an efficient strategy for the synthesis of chiral beta-trifluoromethyl amines|
MASSOLO, ELISABETTA (Primo)
BENAGLIA, MAURIZIO (Corresponding)
ROSSI, SERGIO (Penultimo)
CELENTANO, GIUSEPPE (Ultimo)
|Parole Chiave:||bifunctional catalyst; chiral fluorinated amines; nitroalkenes; reduction; trifluoromethyl derivatives|
|Settore Scientifico Disciplinare:||Settore CHIM/06 - Chimica Organica|
|Data di pubblicazione:||23-feb-2015|
|Digital Object Identifier (DOI):||http://dx.doi.org/10.1002/chem.201405730|
|Appare nelle tipologie:||01 - Articolo su periodico|
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