OXIDATION OF ALKYNES BY HYDROGEN PEROXIDE CATALYZED BY METHYLRHENIUM TRIOXIDE

摘要

The oxidation of alkynes with hydrogen peroxide is catalyzed by methylrhenium trioxide. The reactions can be rationalized by postulating that an oxirene intermediate is formed between a rhenium peroxide and the alkyne. Internal alkynes yield alpha-diketones and carboxylic acids, the latter from the complete cleavage of the triple bonds. Rearrangement products were observed only for aliphatic alkynes. Terminal alkynes gave carboxylic acids and their derivatives and alpha-keto acids as the major products, but their yields varied with the solvent used.