Epoxide ring opening reactions hydrocarbons

Several types of copper-loaded polymer have been prepared. Hydrocarbon spacers were introduced between polystyrene and copper (23). Six synthetically useful copper-promoted reactions including a Diels-Alder reaction, an epoxide ring-opening, and an aryl iodide hydrolysis were examined by using the polymeric catalyst [34]. Use of the copper-loaded polymers often either improved the yield or reduced the reaction time compared with those for conventional copper salts. 

Long-chain derivatives of pyrazolyl pyridines coordinated to MoO(02)2 as 35 may efficiently replace the conventional Mo(CO)e in the oxidation of several double-bond typologies with TBHP, in non-polar hydrocarbon solvents . The epoxidation of cyclopentene and 2,3-dimethyl-2-butene led to the corresponding epoxides, notoriously sensitive to ring opening, in 100% and 87% yield respectively, in isoctane, with 1 hour reaction time. Recent advances in the epoxidation of a-pinene and other terpenes using the Mo-TBHP system have been reported. ... 

The hydrogenolyaia of cyclopropane rings (C—C bond cleavage) has been described on p, 105. In syntheses of complex molecules reductive cleavage of alcohols, epoxides, and enol ethers of 5-keto esters are the most important examples, and some selectivity rules will be given. Primary alcohols are converted into tosylates much faster than secondary alcohols. The tosylate group is substituted by hydrogen upon treatment with LiAlH (W. Zorbach, 1961). Epoxides are also easily opened by LiAlH. The hydride ion attacks the less hindered carbon atom of the epoxide (H.B. Henhest, 1956). The reduction of sterically hindered enol ethers of 9-keto esters with lithium in ammonia leads to the a,/S-unsaturated ester and subsequently to the saturated ester in reasonable yields (R.M. Coates, 1970). Tributyltin hydride reduces halides to hydrocarbons stereoselectively in a free-radical chain reaction (L.W. Menapace, 1964) and reacts only slowly with C 0 and C—C double bonds (W.T. Brady, 1970 H.G. Kuivila, 1968). 

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