Akademik Veri Yönetim Sistemi
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, cilt.4, sa.4, ss.649-658, 1996 (SCI-Expanded)
Rate constants (k(obs)) and reaction orders have been determined for the cathodic reduction in DMF solution of 11 cinnamic acid esters including some derived from chiral alcohols and a dicinnamate derived from trans-cyclohexane-1,2-diol. The cinnamic acid esters typically reduce with high stereoselectivity to all-trans 3,4-diphenylcyclopentanone-2-carboxylate.dagger The enhancement of rates of reaction by addition of water was studied for selected substrates and low energies of activation were found, Changes in the alkoxy or aryloxy groups also caused significant changes in rate and log k(obs) correlated linearly with E degrees values, The results from kinetic experiments were complemented by product studies of reactions aimed at probing reversibility of key reaction steps. The combined evidence is interpreted as unambiguous support for radical anion-radical anion coupling as the key step with complexation with water, prior to coupling, being crucial.