{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Rafiee M"],"funding":["Biological and Environmental Research","NIGMS NIH HHS"],"pagination":["14751-7"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC4863653"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["137(46)"],"pubmed_abstract":["Bicyclic nitroxyl derivatives, such as 2-azaadamantane N-oxyl (AZADO) and 9-azabicyclo[3.3.1]nonane N-oxyl (ABNO), have emerged as highly effective alternatives to TEMPO-based catalysts for selective oxidation reactions (TEMPO = 2,2,6,6-tetramethyl-1-piperidine N-oxyl). Their efficacy is widely attributed to their smaller steric profile; however, electrocatalysis studies described herein show that the catalytic activity of nitroxyls is more strongly affected by the nitroxyl/oxoammonium redox potential than by steric effects. The inexpensive, high-potential TEMPO derivative, 4-acetamido-TEMPO (ACT), exhibits higher electrocatalytic activity than AZADO and ABNO for the oxidation of primary and secondary alcohols. Mechanistic studies provide insights into the origin of these unexpected reacti"],"journal":["Journal of the American Chemical Society"],"pubmed_title":["Electrocatalytic Alcohol Oxidation with TEMPO and Bicyclic Nitroxyl Derivatives: Driving Force Trumps Steric Effects."],"pmcid":["PMC4863653"],"funding_grant_id":["R01 GM100143","R01 GM100143).","DE-FC02-07ER64494"],"pubmed_authors":["Miles KC","Stahl SS","Rafiee M"],"additional_accession":[]},"is_claimable":false,"name":"Electrocatalytic Alcohol Oxidation with TEMPO and Bicyclic Nitroxyl Derivatives: Driving Force Trumps Steric Effects.","description":"Bicyclic nitroxyl derivatives, such as 2-azaadamantane N-oxyl (AZADO) and 9-azabicyclo[3.3.1]nonane N-oxyl (ABNO), have emerged as highly effective alternatives to TEMPO-based catalysts for selective oxidation reactions (TEMPO = 2,2,6,6-tetramethyl-1-piperidine N-oxyl). Their efficacy is widely attributed to their smaller steric profile; however, electrocatalysis studies described herein show that the catalytic activity of nitroxyls is more strongly affected by the nitroxyl/oxoammonium redox potential than by steric effects. The inexpensive, high-potential TEMPO derivative, 4-acetamido-TEMPO (ACT), exhibits higher electrocatalytic activity than AZADO and ABNO for the oxidation of primary and secondary alcohols. Mechanistic studies provide insights into the origin of these unexpected reacti","dates":{"release":"2015-01-01T00:00:00Z","publication":"2015 Nov","modification":"2025-04-22T06:21:47.147Z","creation":"2019-03-27T02:13:28Z"},"accession":"S-EPMC4863653","cross_references":{"pubmed":["26505317"],"doi":["10.1021/jacs.5b09672"]}}