"Activation of the C-H Bond by Electrophilic Attack: Theoretical Study of the Reaction Mechanism of the Aerobic Oxidation of Alcohols to Aldehydes by the Cu(bipy)(2+)/2,2,6,6-Tetramethylpiperidinyl-1-oxy Cocatalyst System"
- Title
- "Activation of the C-H Bond by Electrophilic Attack: Theoretical Study of the Reaction Mechanism of the Aerobic Oxidation of Alcohols to Aldehydes by the Cu(bipy)(2+)/2,2,6,6-Tetramethylpiperidinyl-1-oxy Cocatalyst System"
- Authors
- Michel, C; Belanzoni, P; Gamez, P; Reedijk, J; Baerends, EJ; null
- Date Issued
- 2009-12
- Publisher
- AMER CHEMICAL SOC
- Abstract
- We have investigated the reaction mechanism of the selective aerobic oxidation of primary alcohols into aldehydes using a bipy-copper complex and the 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO) radical as cocatalysts (Gamez et al. Chem. Commun. 2003, 2412-2415) and compared it to the well-known oxidation by the TEMPO+ ion. Our theoretical investigation shows that (a) the oxidation of alcohols to aldehydes by uncoordinated TEMPO+ takes place by electrophilic attack on the C-H-alpha bond of the alcohol
(b) the Cu(bipy)(2+) complex has two functions, namely, (1) it acts as a template that brings TEMPO and the (deprotonated) alcohol in proximity by coordinating these moieties in adjacent coordination sites, and (2) it oxidizes the TEMPO radical to (coordinated) TEMPO+ ion. The H abstraction from alcohol by TEMPO+ then proceeds as an intramolecular reaction, very much analogous to one of the reaction pathways with free TEMPO+ and with a remarkably low barrier. We stress that compared to other A-H bonds (A=C, N, O, F), the relatively high-lying C-H bonds are particularly susceptible to electrophilic attack, and notably the C-H-alpha bond next to the O in an alcohol is so because it is pushed up by an 0 lone pair Electrophilic attack, being common to the particular catalytic system studied in this paper and the well-known biotic and abiotic oxidation catalysis by heme and non-heme complexes of the ferryl ((FeO2+)-O-IV) ion, appears to be a unifying electronic structure principle of C-H-alpha hydroxylation and oxidation reactions.
- Keywords
- COPPER-CATALYZED OXIDATION; GALACTOSE-OXIDASE; SELECTIVE OXIDATION; SCREENING MODEL; SOLVATION; EFFICIENT; KETONES; OXYGEN; RADICALS; LIQUID
- URI
- https://oasis.postech.ac.kr/handle/2014.oak/27694
- DOI
- 10.1021/IC902155M
- ISSN
- 0020-1669
- Article Type
- Article
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- There are no files associated with this item.
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