Selective oxidation of primary alcohols mediated by nitroxyl radical in aqueous solution. Kinetics and mechanism

article


Nooy, A.E.J. de

Besemer, A.C.

Bekkum, H. van
The kinetics of the TEMPO-mediated oxidation of methyl α-D- glucopyranoside to sodium methyl α-D-glucopyranosiduronate were studied. An intermediate was found which was identified as the hydrated aldehyde. This was oxidised in the same manner as the alcohol, with pseudo first order rate constants ratio k(obs,ald)/k(obs,alc) = 7. The reaction mechanism is discussed with emphasis on steric factors and compared to literature data. Two different reaction pathways are postulated; under basic reaction conditions via a cyclic transition state 3 and under acid reaction conditions through an acyclic transition state 4.
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2,2,6,6 tetramethylpiperidine 1 oxylalcoholaldehyde derivativealpha methylglucosideglucose derivativemethyl alpha d glucopyranosiduronic acidradicalunclassified drugalcohol oxidationaqueous solutionarticlechemical reaction kineticspriority journalreaction analysis
TNO Identifier
233016
Repository link
https://resolver.tno.nl/uuid:7a3922a7-3422-4ded-aa06-954ec70a56e3
ISSN
00404020
Source
Tetrahedron, 51(29), pp. 8023-8032.
Pages
8023-8032
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