Oxirane openings structures

Deoxy-4-fluoro-D-fructose (552) was prepared (59%) by fermentation of 3-deoxy-3-fluoro-D-mannitol with Gluconobacter oxydans. The structure of 552 (fi-T) form) was confirmed by the n.m.r. spectrum, which resembles that of 4-deoxy-4-fluoro-Q -D-sorbopyranose (553) 552 was identical with one of the products obtained from the oxirane-ring opening of 3,4-anhy-dro-l,2-0-isopropylidene- -D-tagatopyranose with KHFj. 

This contrasts to the situation for the oxirane radical cation, for which the nature of the species observed experimentally in frozen matrices was long disputed [63], Tomasi and his group [64] first reported calculations on the fate of the oxirane radical cation produced by vertical excitation. Later calculations [65-67] all agree that the C- C ring-opened product 15 is formed from the oxirane radical cation with a low activation energy and that this is the structure observed in frozen matrices. Remarkably, the prototype W.-H. electrocyclic... 

Carbon-13 shift values of parent heterocycloalkanes [408] collected in Table 4.61 are essentally determined by the heteroatom electronegativity, in analogy to the behavior of open-chain ethers, acetals, thioethers, thioacetals, secondary and tertiary amines. Similarly to cyclopropanes, three-membered heterocycloalkanes (oxirane, thiirane, and azirane derivatives) display outstandingly small carbon-13 shift values due to their particular bonding state. Empirical increment systems based on eq. (4.1) permit shift predictions of alkyl- and phenyl-substituted oxiranes [409] and of methyl-substituted tetrahydropyrans, tetrahydrothiapyrans, piperidines, 1,3-dithianes, and 1,3-oxathianes [408], respectively. Methyl increments of these heterocycloalkanes are closely related to those derived for cyclohexane (Table 4.7) due to common structural features of six-membered rings. 

In recent years there has been a growing interest in the use of carbonyl ylides as 1,3-dipoles for total synthesis.127-130 Their dipolar cycloaddition to alkenic, alkynic and hetero multiple bonded dipolaro-philes has been well documented.6 Methods for the generation of carbonyl ylides include the thermal and photochemical opening of oxiranes,131 the thermal fragmentation of certain heterocyclic structures such as A3-l,3,4-oxadiazolines (141) or l,3-dioxolan-4-ones132-134 (142) and the reaction of carbenes or car-benoids with carbonyl derivatives.133-138 Formation of a carbonyl ylide by attack of a rhodium carbenoid... 

Photoinitiated epoxy crosslinking is generally based (with one exception on cationic ring-opening polymerization of the oxirane group, yielding polyether structures. 

---