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. MassoloPrimo
;M. Benaglia
Secondo
;M. Orlandi;S. RossiPenultimo
;G. CelentanoUltimo
2015
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.File | Dimensione | Formato | |
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