The diastereoselective electrochemical carboxylation of chiral N-(2-bromoacyl)oxazolidin-2-ones has been studied. This reaction was carried out by cathodic reduction of the C-Br bond, in the presence of carbon dioxide, followed by treatment with diazomethane. The yields and the diastereomeric ratio of the two epimeric alkylmalonic acid derivatives are strongly affected by various factors: solvent-supporting electrolyte system, temperature, electrode material, electrolysis conditions, oxazolidinone moiety. The higher yields (88%) were obtained starting from N-(2-bromopropionyl)- 4R-phenyloxazolidin-2-one 1a, but with poor diastereoselectivity (61:39). The two epimers were easily separated by flash chromatography. The best results were achieved using a different chiral auxiliary: Oppolzer’s camphor sultam. Starting from 1j a good yield in carboxylated product was obtained (80%) with excellent diastereoselectivity (98:2). These chiral alkylmalonic acid derivatives are valuable building blocks in the synthesis of molecules with biological activity and of chiral propane-1,3-diols derivatives.

Diastereoselective electrochemical carboxylation of chiral α-bromocarboxylic acid derivatives: an easy access to unsymmetrical alkylmalonic ester derivatives / Feroci, Marta; M., Orsini; L., Palombi; G., Sotgiu; Colapietro, Marcello; Inesi, Achille. - In: JOURNAL OF ORGANIC CHEMISTRY. - ISSN 0022-3263. - STAMPA. - 69:(2004), pp. 487-494. [10.1021/jo0343836]

Diastereoselective electrochemical carboxylation of chiral α-bromocarboxylic acid derivatives: an easy access to unsymmetrical alkylmalonic ester derivatives

FEROCI, Marta;COLAPIETRO, Marcello;INESI, ACHILLE
2004

Abstract

The diastereoselective electrochemical carboxylation of chiral N-(2-bromoacyl)oxazolidin-2-ones has been studied. This reaction was carried out by cathodic reduction of the C-Br bond, in the presence of carbon dioxide, followed by treatment with diazomethane. The yields and the diastereomeric ratio of the two epimeric alkylmalonic acid derivatives are strongly affected by various factors: solvent-supporting electrolyte system, temperature, electrode material, electrolysis conditions, oxazolidinone moiety. The higher yields (88%) were obtained starting from N-(2-bromopropionyl)- 4R-phenyloxazolidin-2-one 1a, but with poor diastereoselectivity (61:39). The two epimers were easily separated by flash chromatography. The best results were achieved using a different chiral auxiliary: Oppolzer’s camphor sultam. Starting from 1j a good yield in carboxylated product was obtained (80%) with excellent diastereoselectivity (98:2). These chiral alkylmalonic acid derivatives are valuable building blocks in the synthesis of molecules with biological activity and of chiral propane-1,3-diols derivatives.
carboxylation; carbon dioxide; cathodic reduction; N-(2-bromoacyl)oxazolidin-2-ones; alkylmalonic acid derivatives
01 Pubblicazione su rivista::01a Articolo in rivista
Diastereoselective electrochemical carboxylation of chiral α-bromocarboxylic acid derivatives: an easy access to unsymmetrical alkylmalonic ester derivatives / Feroci, Marta; M., Orsini; L., Palombi; G., Sotgiu; Colapietro, Marcello; Inesi, Achille. - In: JOURNAL OF ORGANIC CHEMISTRY. - ISSN 0022-3263. - STAMPA. - 69:(2004), pp. 487-494. [10.1021/jo0343836]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11573/240171
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