Combined electrochemical/enzymic method for in situ regeneration of NADH based on cathodic reduction of cyclic disulfides

Recent Trends in Biomimetic NADH Regeneration

“…The first electro-enzymatic regeneration of NAD(P)H was reported by the group of Whitesides. For this purpose, they relied on a tungsten cathode to reduce either a disulfide to the corresponding dithiol [13] or methyl viologen [14] to provide the reducing equivalents for the enzymatic reduction of NAD ? or nicotinamide adenine dinucleotide phosphate (NADP ? )…”

Enantioselective electrochemical oxidation of enol acetates using a chiral supporting electrolyte

“…The first electron transfer from 1 to an anode may generate a cation radical (5), which is subjected to alternative two pathways A or B. In path A, nucleophilic attack of an acetoxy anion to the 2-position of 5 followed by the second electron transfer takes place to generate diacetoxy carbocation (7), which exclusively gives the desired 2-acetoxy ketone (2). The electron-withdrawing character of the 7-methoxy group may accelerate this path A by distribution of the positive charge on the 1-carbon atom to the 2-carbon atom.…”

“…Many of the successful studies for this purpose have focused on enantioselective anodic oxidation using a chemically modified electrode system using Teflon-plated electrodes, 1,2 montmorillonitemodified electrodes, 3 and chiral TEMPO modified polyacrylate-coated graphite electrodes, [4][5][6] although synthetic utility of these methods is considerably limited because of the difficulty in preparation and recycling use of chemically modified electrodes and some lack in reproducibility of the results. NAD/NADH-mediated indirect electrolysis 7 and diastereoselective electrochemical asymmetric induction [8][9][10] have also been reported. On the other hand, some attempts at electroreduction of some aromatic ketones using chiral supporting electrolytes led to poor enantioselectivity (ee 1-19%) in the formation of the corresponding 1-aryl alcohol.…”

Tailoring nanoarchitectonics to control the release profile of payloads

“…The electrochemical reduction was also proved to be useful for the cleavage of the stable cyclic disulfides to the corresponding dithiols. 42 To further investigate the redox-responsive properties, silica nanocapsules were treated in a sequential reductionoxidation-reduction (see Fig. 2c).…”