Current Organic Chemistry - Volume 9, Issue 1, 2005

This review deals with the metal promoted asymmetric ring opening of achiral epoxides using achiral carbon-, nitrogen-, oxygen-, sulphur- and halogen-containing nucleophiles. The use of chiral bases in the asymmetric deprotonation of achiral epoxides yields chiral allylic alcohols. Finally, kinetic resolution of racemic epoxides can be achieved using chiral metal complexes.

Supercritical carbon dioxide is ideally suited as reaction medium for catalytic oxidations of organic substrates, and it may be exploited as one of the most promising strategies to realize some fundamental chemical transformations under environmentally benign conditions. The use of supercritical carbon dioxide as solvent for unselective hydrocarbons auto-oxidations is extensively described in the literature. Conversely, only a limit Read More

A new method of 5-chloropyrazine-2-carbonitrile preparation in a regioselective fashion and the study of the coupling of the pyrazine ring with variously substituted benzenethiols are described. A radical-ionic mechanism of this coupling, carried out in the presence of a heterogeneous copper catalyst, has been proposed. The reactivity of the substituted chloropyrazines is correlated to the calculated values of electronic Read More

As phosphoryl transfer reactions are ubiquitous in biological chemistry, organic chemists have been very interested in the mechanisms of phosphate and phosphinate esters. Physical organic chemistry methods, including stereochemical studies, linear free energy relationships, and, most recently, heavy-atom kinetic isotope effects, have been used in the quest for mechanistic information about the chemistry of thes Read More

A critical review of applications of chlorine kinetic isotope effects in studies of organic reactions mechanisms is presented. Reports from the last five years are considered. During this time chlorine kinetic isotope effects were applied mainly in studies of elimination reactions and nucleophilic substitution reactions. In several cases chemical models were also used as models of the intrinsic kinetic isotope effects in several enzy Read More