Diallyl carbonate, oxidation

The slow oxidation of primary alcohols, particularly MeOH, is utilized for the oxidation of allylic or secondary alcohols with allyl methyl carbonate without forming carbonates of the alcohols to be oxidized. Allyl methyl carbonate (564) forms 7r-allylpalladium methoxide, then exchange of the methoxide with a secondary or allylic alcohol 563 present in the reaction medium takes place to form the 7r-allylpalladium alkoxide 565, which undergoes elimination of j3-hydrogen to give the ketone or aldehyde 566. The lactol 567 was oxidized selectively with diallyl carbonate to the lactone 568 without attacking the secondary alcohol in the synthesis of echinosporin[360]. 

The oxidation of butadiene, diallyl carbonate, or diallyl ether gives the products of monoepoxidation with selectivities of 85% and higher when the ratio diene/H202 is 2.5 (Table VIII). The diepoxides are formed in larger amounts when the diene/H202 ratio is 1. 

Indeed the slow oxidation of primary alcohols enables the use of external allylating agents as oxidants. For example, unprotected lactol 102 was selectively oxidized with diallyl carbonate 103 to yield lactone 104. Lactone 104 was subsequently used in the synthesis of echinosporin. 

Caustic potash Chloric acid Chlorine, dry Chloroacetic acid Chloroacetone Chloroform Chlorosilanes Chlorosulfonic acid Chromic acid Chromic chloride Chromic fluorides Chromic hydroxide Chromic nitrates Chromic oxides Chromic phosphate Chromic sulfate Coconut oil Cod liver oil Coke oven gas Copper carbonate Copper chloride Copper cyanide Copper nitrate Copper oxide Copper sulfate Corn oil Coconut oil Cresylic acid Crude oil Cutting oils Cyclohexane Cyclohexanol Cyclohexanone Cyclohexene Denatured alcohol Detergent solution Dex train Dextrose Diacetone Diallyl ether Diallyl phthalate Dichloroacetic acid Dichloroaniline o-Dichlorobenzene Dichloroethane Dichloroethylene Dichloromethane Dichlorophenol Diesel oil... 

The oxidative mono- or diallylation of 1,3-dicarbonyl compounds by allylic silanes proceeds in the presence of VO(OEt)Cl2 as shown in Scheme 2.53 [116]. The 1,3-dicarbonyl compounds formally act as electrophiles in this oxidative carbon-carbon bond forming reaction. 

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