The Amano PS lipase-catalyzed acetylation of 2-hydroxymethylaziridines 1a–e has been investigated in order to evaluate the effect of ring substituents on the enantioselectivity of the reaction and to assess the stereochemical preference of the enzyme. N-Benzyl-3-substituted cis-aziridines displayed high enantioselectivity and higher E values were found when the bulkiness of the substituent in position 3 was increased. In contrast, the corresponding trans isomers showed only poor enantioselectivity, regardless of the steric hindrance of the substituent at C3. Removal of the N-benzyl group proved to be detrimental to the enantioselectivity. In addition, desymmetrization of meso dimethanolic cis-aziridine 1f was successfully accomplished, and the corresponding monoacetylated product 2f, which is related to a key intermediate used in the total synthesis of the mitomycin antibiotic FR-900482, was obtained in excellent yield and nearly enantiomerically pure form. Moreover, the absolute configuration of enantiomerically pure cis-aziridines was determined by chemical correlation and/or chiroptical techniques, thus showing the stereochemical preference of Amano PS lipase for the 2S enantiomer.

Lipase-Catalyzed Resolution and Desymmetrization of 2-Hydroxymethylaziridines / Davoli, Paolo; Caselli, Emilia; Bucciarelli, Maria; Forni, Arrigo; Torre, Giovanni; Prati, Fabio. - In: JOURNAL OF THE CHEMICAL SOCIETY. PERKIN TRANSACTIONS. 1. - ISSN 1472-7781. - STAMPA. - 17(2002), pp. 1948-1953.

Lipase-Catalyzed Resolution and Desymmetrization of 2-Hydroxymethylaziridines

DAVOLI, Paolo;CASELLI, Emilia;BUCCIARELLI, Maria;FORNI, Arrigo;TORRE, Giovanni;PRATI, Fabio
2002

Abstract

The Amano PS lipase-catalyzed acetylation of 2-hydroxymethylaziridines 1a–e has been investigated in order to evaluate the effect of ring substituents on the enantioselectivity of the reaction and to assess the stereochemical preference of the enzyme. N-Benzyl-3-substituted cis-aziridines displayed high enantioselectivity and higher E values were found when the bulkiness of the substituent in position 3 was increased. In contrast, the corresponding trans isomers showed only poor enantioselectivity, regardless of the steric hindrance of the substituent at C3. Removal of the N-benzyl group proved to be detrimental to the enantioselectivity. In addition, desymmetrization of meso dimethanolic cis-aziridine 1f was successfully accomplished, and the corresponding monoacetylated product 2f, which is related to a key intermediate used in the total synthesis of the mitomycin antibiotic FR-900482, was obtained in excellent yield and nearly enantiomerically pure form. Moreover, the absolute configuration of enantiomerically pure cis-aziridines was determined by chemical correlation and/or chiroptical techniques, thus showing the stereochemical preference of Amano PS lipase for the 2S enantiomer.
17
1948
1953
Lipase-Catalyzed Resolution and Desymmetrization of 2-Hydroxymethylaziridines / Davoli, Paolo; Caselli, Emilia; Bucciarelli, Maria; Forni, Arrigo; Torre, Giovanni; Prati, Fabio. - In: JOURNAL OF THE CHEMICAL SOCIETY. PERKIN TRANSACTIONS. 1. - ISSN 1472-7781. - STAMPA. - 17(2002), pp. 1948-1953.
Davoli, Paolo; Caselli, Emilia; Bucciarelli, Maria; Forni, Arrigo; Torre, Giovanni; Prati, Fabio
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11380/457167
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