The asymmetric oxidation of 2-substituted dithianes, dithiolanes and oxathiolanes catalyzed by cyclohexanone monooxygenase (CMO) has been examined. The introduction of substituents at the C-2 causes a decrease of the e.e. with the exception of 2-benzoyl-1,3-dithiane monosulfoxide (90% e.e). With 2-monosubstituted dithioacetals CMO yields preferentially or exclusively the trans diastereoisomer. The binding of the 1,3-dithioacetals at the active site of the enzyme is not only controlled by the sterical hindrance of the substituents in position 2 but also by the configuration at C-2. The stereoselectivity of CMO has been compared with that reported for microsomal flavin and cytochrome P-450 monooxygenases.
Enantio and diastereoselectivity of cyclohexanone monooxygenase catalyzed oxidation of 1,3-dithioacetals / S. Colonna, N. Gaggero, G. Carrea, P. Pasta. - In: TETRAHEDRON-ASYMMETRY. - ISSN 0957-4166. - 7:2(1996), pp. 565-570. [10.1016/0957-4166(96)00040-7]
Enantio and diastereoselectivity of cyclohexanone monooxygenase catalyzed oxidation of 1,3-dithioacetals
S. ColonnaPrimo
;N. GaggeroSecondo
;
1996
Abstract
The asymmetric oxidation of 2-substituted dithianes, dithiolanes and oxathiolanes catalyzed by cyclohexanone monooxygenase (CMO) has been examined. The introduction of substituents at the C-2 causes a decrease of the e.e. with the exception of 2-benzoyl-1,3-dithiane monosulfoxide (90% e.e). With 2-monosubstituted dithioacetals CMO yields preferentially or exclusively the trans diastereoisomer. The binding of the 1,3-dithioacetals at the active site of the enzyme is not only controlled by the sterical hindrance of the substituents in position 2 but also by the configuration at C-2. The stereoselectivity of CMO has been compared with that reported for microsomal flavin and cytochrome P-450 monooxygenases.Pubblicazioni consigliate
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