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 97î. 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. [10.1002/chem.201405730]

Enantioselective organocatalytic reduction of beta-trifluoromethyl nitroalkenes: an efficient strategy for the synthesis of chiral beta-trifluoromethyl amines

E. Massolo
Primo
;
M. Benaglia
Secondo
;
M. Orlandi;S. Rossi
Penultimo
;
G. Celentano
Ultimo
2015-02-23

Abstract

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 97î. 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.
bifunctional catalyst; chiral fluorinated amines; nitroalkenes; reduction; trifluoromethyl derivatives
Settore CHIM/06 - Chimica Organica
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/2434/322774
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