965-40-2Relevant academic research and scientific papers
Electrocatalytic Reduction of C-C π-Bonds via a Cobaltocene-Derived Concerted Proton-Electron Transfer Mediator: Fumarate Hydrogenation as a Model Study
Derosa, Joseph,Garrido-Barros, Pablo,Peters, Jonas C.
supporting information, p. 9303 - 9307 (2021/07/19)
Reductive concerted proton-electron transfer (CPET) is poorly developed for the reduction of C-C π-bonds, including for activated alkenes that can succumb to deleterious pathways (e.g., a competing hydrogen evolution reaction or oligomerization) in a standard electrochemical reduction. We demonstrate herein that selective hydrogenation of the C-C π-bond of fumarate esters can be achieved via electrocatalytic CPET (eCPET) using a CPET mediator comprising cobaltocene with a tethered Br?nsted base. High selectivity for electrocatalytic hydrogenation is observed only when the mediator is present. Mechanistic analysis sheds light on two distinct kinetic regimes based on the substrate concentration: low fumarate concentrations operate via rate-limiting CPET followed by an electron-transfer/proton-transfer (ET/PT) step, whereas high concentrations operate via CPET followed by a rate-limiting ET/PT step.
NONCHAIN CONVERSION OF alpha -DIKETONES AND TRANSACYLATION OF CARBOXYLIC-ACID ANHYDRIDES UNDER AUTOXIDATION CONDITIONS.
Perkel',Freidin,Neginskaya,Stolyankova,Ivanova
, p. 1444 - 1449 (2007/10/02)
The present investigation produced the following conclusion. The oxidation of 8,9-hexadecanedione by peroxylauric acid in benzene solution conforms to the kinetic equation for a second-order reaction. The oxidation is accompanied by transacylation of the caprylic anhydride formed with lauric acid. The anhydrides formed by transcylation take part in the formation of ester products of autoxidation. Lauric acid actively catalyzes the reaction of 8,9-hexadecanedione with peroxylauric acid.
