939-48-0Relevant articles and documents
Rapid long range intramolecular electron transfer within a steroid molecule with two electron binding groups
Huddleston, R. Kurt,Miller, John R.
, p. 5337 - 5344 (1983)
Intramolecular electron tarnsfer has been observed to have occurred in less than 100 ns in a steroid molecule having two distinct electron binding groups separated by distances distributed from 7-11 Angstroem.Experiments were carried out in organic glasses at 77 K with pulse radiolysis techniques to create trapped electrons which were captured by a group on one end of the steroid molecule.Although one of the groups, benzoate, is held to the steroid spacer by a flexible linkage, the rigidity of the glassy matrices prevented movement to alter the initial distance.Interestingly, no effects of distance were seen: all ET processes appeared to have occurred much faster than our 100 ns time resolution, consistent with measurements of the rate of intermolecular electron transfer between the same functional groups in random solutions.Solvation energetics, on the other hand, had a remarkable influence on the extent and direction of electron transfer.A change in solvent polarity was observed to reverse the direction of electron transfer.Evidence was obtained for a distribution of solvation environments for ions in glasses which may be as broad as 0.15 eV.
Electrochemical esterification via oxidative coupling of aldehydes and alcohols
Smeyne, Dylan,Verboom, Katherine,Bryan, Maria,LoBue, James,Shaikh, Abid
supporting information, (2021/03/26)
An electrolytic method for the direct oxidative coupling of aldehydes with alcohols to produce esters is described. Our method involves anodic oxidation in presence of TBAF as supporting electrolyte in an undivided electrochemical cell equipped with graphite electrodes. This method successfully couples a wide range of alcohols to benzaldehydes with yields ranging from 70 to 90%. The protocol is easy to perform at a constant voltage conditions and offers a sustainable alternative over conventional methods.
PCl3-mediated transesterification and aminolysis of tert-butyl esters via acid chloride formation
Wu, Xiaofang,Zhou, Lei,Li, Fangshao,Xiao, Jing
, p. 491 - 497 (2021/01/20)
A PCl3-mediated conversion of tert-butyl esters into esters and amides in one-pot under air is developed. This novel protocol is highlighted by the synthesis of skeletons of bioactive molecules and gram-scale reactions. Mechanistic studies revealed that this transformation involves the formation of an acid chloride in situ, which is followed by reactions with alcohols or amines to afford the desired products.
