Efficient, copper-catalyzed, aerobic oxidation of primary alcohols

Angewandte Chemie - International Edition

Volumn 43, Issue 12, 2004, Pages 1588-1591

  Markó, István E ^a   Gautier, Arnaud ^a   Dumeunier, Raphaël ^a   Doda, Kanae ^a   Philippart, Freddi ^a   Brown, Stephen M ^b   Urch, Christopher J ^c  

^a UNIVERSITÉ CATHOLIQUE DE LOUVAIN   (Belgium)

^b ASTRAZENECA   (United Kingdom)

^c JEALOTT S HILL RESEARCH STATION   (United Kingdom)

Author keywords

Aerobic oxidation; Alcohols; Aldehydes; Molecular oxygen; Oxidation

Indexed keywords

ALDEHYDES; CARBOXYLIC ACIDS; CATALYSIS; OXIDATION;

CATALYTIC AMOUNTS; CUCL;

ALCOHOLS;

ALCOHOL DERIVATIVE; COPPER;

ARTICLE; CATALYSIS; ORGANIC CHEMISTRY; OXIDATION; PRODUCTIVITY; QUANTUM YIELD;

ALCOHOLS; CATALYSIS; COPPER; KETONES; MOLECULAR STRUCTURE; OXIDANTS; OXIDATION-REDUCTION;

EID: 4544344165     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200353458     Document Type: Article

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48. The overoxidation of the aldehyde into the corresponding carboxylic acid has never been observed with this aerobic oxidation protocol. Whilst no proper explanation can be provided at this stage, it is possible that the copper catalyst protects the aldehyde towards further reaction with dioxygen. A similar observation has been reported by Sheldon et al.[7a]
49. Whilst quantitative conversion of 3 into 4 occurred in the absence and presence of 7 mol% NMI, the oxidation of 3 proceeded more slowly in the presence of this additive (87% conversion after 30 min in the absence of NMI and 75% conversion after 30 min in the presence of NMI). The coordination of NMI to copper results in a slower exchange with the excess DBAD and hence, in a longer reaction time.
50. Studies performed on the anaerobic version of this catalytic system revealed that aliphatic primary alcohols were oxidized with the same efficiency as all the other classes of alcohols, thus ruling out complexes A, B, and E as the culprit for the decomposition pathway. Whilst we could not experimentally rule out complex D, coordination of an alcohol to D should involve the participation of a pentacoordinated copper species. Whilst these are not uncommon, their formation requires a higher activation energy than the coordination to C.
51. 2 is unable to displace the alkoxo ligand from the copper complex G.
52. We have previously demonstrated[11a] that G was not a competent catalyst in the aerobic oxidation protocol when R = alkyl. Under anaerobic conditions, that is, in the presence of 1 equiv DBAD, G can efficiently regenerate the loaded ternary complex A and smooth oxidation ensues.
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55. In full accord with this mechanistic rationale, the use of NMI and other heterocyclic nitrogen derivatives allows the preferential kinetic oxidation of primary aliphatic alcohols over secondary ones. Whilst the selectivities are not yet perfect, initial experiments have shown that the nature of the additive strongly affects the selectivity of this oxidation.