Cyclododecene oxides

Trans-Cyclododecene oxide /rans- 13-Oxabicyclo[ 10.1.0]tridecane (8,9) (4683-60-7)... 

Nozaki and Yamamoto reported a novel method for regiospecific isomerization of epoxides to allylic alcohols based on diethylaluminum 2,2,6,6-tetramethylpiperidide (DATMP) which can be prepared in situ from Et2AlCl and lithium 2,2,6,6-tetramethylpiperidide (LiTMP) (molar ratio 1 1) in benzene at 0 °C for 30 min [119], Reaction of DATMP (4 equiv.) with ( )-cyclododecene oxide in benzene at 0 °C for 3 h produced ( )-2-cyclododecen-l-ol in 90 % yield. Interestingly, the reaction of diepoxide 121, a useful synthetic intermediate in the preparation of Cig-Cecropia juvenile hormone, with DATMP furnished the triol 122 in 41 % yield (Sch. 83). 

In contrast both cis- and /ran.s-cyclododecene oxide (8,9) on treatment with base give as the major product the allylic alcohol, uwis-2-cyclododecenol (10).3b This reaction evidently involves elimination of a hydrogen fi to the oxide ring. 

Deoxygenation of epoxides (4, 569-570). Detailed instructions for deoxygenation of rrans-cyclododecene oxide (1) are available. ... 

Dienes from epoxides. In refluxing dichloroethane in the presence of triethyl-amine, epoxides undergo a double-elimination reaction, giving conjugated dienes in good yields. Crowded epoxides remain unchanged thus, the mixture of cis- and frani-cyclododecene oxides affords a clean mixture of (IE, 3Z)-cyclododecadiene and rran -cyclododecene oxide (50% yield). 

The dimethanesulphonates of 1,2-diols are rapidly converted into alkenes by treatment with sodium anthracene or sodium naphthalene anion-radicals dimesylates of cis- and trans-cyclo-octane-l,2-diols apparently both give cis-Cyclododecene oxides give olefins with practically complete retention of with iron pentacarbonyl thus (119) gives cis-cyclohepiene (35%). ... 

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