Oxiranes 1,2-diol formation

The epoxidized esters produeed by in situ epoxidation using formic acid, under the reaction conditions described above show high oxirane values and low iodine values. In addition, they present satisfactory aspect and color. The absence of a hydroxyl group (<0.1) indicates a negligible oxirane cleavage, in other words, a very limited diol formation. The chemical characteristics of the epoxidized materials are shown in Table 4. 

When 1,2-diols are subjected to the same reaction conditions required for the formation of sulphonic esters, oxiranes are produced [27]. Presumably, the mono ester is initially formed and, under the basic conditions, intramolecular elimination occurs to produce the oxirane. Partial hydrolysis and ring-closure of a,p-di(tosyloxy) compounds under basic phase-transfer catalytic conditions provides a convenient route to carbohydrate oxiranes [e.g. 28, 29]. Oxiranes have been produced by an analogous method via carbonate esters from partially protected carbohydrates [30],... 

In contrast to the relative chemical stability of mono-epoxides, diol epoxides of fatty acids (10.52), which are formed from di-epoxides by EH, are subject to a different fate. In such metabolites, intramolecular nucleophilic substitution may occur, such that oxirane opening is accompanied by formation of a tetrahydrofuran ring [134], Such reactions of intramolecular nucleophilic substitution are discussed in detail in Sect. 11.9. In the case of diol epoxides of fatty acids, the resulting tetrahydrofuran-diols (10.53) are part of a much larger ensemble of oxygenated metabolites of fatty acids, the potential cytotoxicities of which are being evaluated [135]. 

In the pH range of 5 - 10, H20-catalyzed hydrolysis is the predominant mechanism (see Fig. 10.11, Pathway b), resulting in the formation of the (8R,9R)-dihydrodiol (10.133, Fig. 10.30). Thus, aflatoxin B1 exo-8,9-epoxide is possibly the most reactive oxirane of biological relevance. Such an extreme reactivity is mostly due to the electronic influence of 0(7), as also influenced by stereolectronic factors, i.e., the difference between the exo- and endo-epoxides. The structural and mechanistic analogies with the dihydro-diol epoxides of polycyclic aromatic hydrocarbons (Sect. 10.4.4) are worth noting. 

The hydrolytic kinetic resolution of racemic terminal epoxides using metal salen catalysts is one of the premier methods for the formation of enantioenriched oxiranes and/or 1,2-diols, e.g., <1997SCI936, 1998JOC6776, 2000AGE3604, 2002JA1307>. 

Oxiranes cannot be prepared directly from 1,2-diols by dehydration. Formation of the oxirane intermediate has been studied in connection with the mechanism of the pinacolic rearrangement. Oxiranes can be prepared stereoselectively from the acetals and ketals of 1,2-diols. D-(+)-2,3-epoxybutane has been obtained from an optically active diol via conversion of the ketal 64 to a halohydrin ester (Eq. 52). ... 

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