Alcohol oxidation is the conversion of a primary or secondary alcohol into the corresponding carbonyl compound—an aldehyde, ketone, or, under further oxidation of a primary alcohol, a carboxylic acid—by removal of hydrogen from the carbinol carbon and the hydroxyl group [1][2]. In catalysis and oxidation reactions the concept is bounded by that two-electron (or equivalent hydrogen-transfer) change at the alcohol carbon, and it excludes combustion of the entire molecule to CO2 as the defining event. Essential features are an oxidant or acceptor that takes up the extracted hydrogen or electrons, a catalyst that mediates the transfer, and a chemoselectivity that stops at a chosen oxidation level. Homogeneous acceptorless dehydrogenative oxidation releases H2 and leaves the carbonyl without a sacrificial oxidant [3]. Aerobic and electrocatalytic variants couple alcohol oxidation to O2 reduction or to anodic electron flow, often through a mediator that shuttles electrons and protons [2][4]. Heterogeneous gold clusters and plasmon-activated semiconductors provide surface pathways in which the alcohol adsorbs, loses hydrogen, and desorbs as the carbonyl [2]. The concept is distinguished from alkane C–H oxidation by the pre-existing C–O bond of the alcohol, and from oxidative esterification by termination at the carbonyl (or acid) rather than at an ester.
- alcohol oxidation
- carbonyl formation
- dehydrogenation
- aerobic oxidation
Alcohol Consumption and Health Effects • Pathology and Forensic Medicine • Medicine • Health Sciences
References
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- Hironori Tsunoyama; Hidehiro Sakurai; Yuichi Negishi; Tatsuya Tsukuda; Size-Specific Catalytic Activity of Polymer-Stabilized Gold Nanoclusters for Aerobic Alcohol Oxidation in Water. J. Am. Chem. Soc. 2005, 127, 9374-9375, 10.1021/ja052161e.
- Robert H. Crabtree; Homogeneous Transition Metal Catalysis of Acceptorless Dehydrogenative Alcohol Oxidation: Applications in Hydrogen Storage and to Heterocycle Synthesis. Chem. Rev. 2017, 117, 9228-9246, 10.1021/acs.chemrev.6b00556.
- Artavazd Badalyan; Shannon S. Stahl; Cooperative electrocatalytic alcohol oxidation with electron-proton-transfer mediators. Nature 2016, 535, 406-410, 10.1038/nature18008.