Enantioselective electrocatalytic oxidation of racemic sec-alcohols using a chiral 1-azaspiro[5.5]undecane- N-oxyl radical

Nitroxyl radical (6 S,7 R,10 R)-4-acetylamino-2,2,7-trimethyl-10-isopropyl-1-azaspiro[5.5]-undecane- N-oxyl reveals a reversible redox peak in cyclic voltammetry at + 0.62 V vs. Ag/AgCl. A preparative electrocatalytic oxidation of racemic sec-alcohols on the nitroxyl radical yielded mixtures of 51.4...

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Published inTetrahedron letters Vol. 40; no. 35; pp. 6469 - 6472
Main Authors Kashiwagi, Yoshitomo, Kurashima, Futoshi, Kikuchi, Chikara, Anzai, Jun-ichi, Osa, Tetsuo, Bobbitt, James.M
Format Journal Article
LanguageEnglish
Published OXFORD Elsevier Ltd 27.08.1999
Elsevier
Subjects
Chemistry
Chemistry, Organic
electrochemical reactions
enantiomeric purity
nitoxides
Physical Sciences
resolution
Science & Technology
electrochemical reactions
enantiomeric purity
resolution
nitoxides
SALTS
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Summary:Nitroxyl radical (6 S,7 R,10 R)-4-acetylamino-2,2,7-trimethyl-10-isopropyl-1-azaspiro[5.5]-undecane- N-oxyl reveals a reversible redox peak in cyclic voltammetry at + 0.62 V vs. Ag/AgCl. A preparative electrocatalytic oxidation of racemic sec-alcohols on the nitroxyl radical yielded mixtures of 51.4 – 63.9 % ketones and 36.1 – 48.6 % alcohols by 10 h of electrolysis. The current efficiency and turnover number of the reactions were 85.6 – 87.9 % and 20.6 – 25.6, respectively. The enantiopurity of the remaining ( R)-isomers was 50 – 70 % and the S values as a selective factor was 4.1 – 4.6. Graphic
ISSN:0040-4039
1873-3581
DOI:10.1016/S0040-4039(99)01325-8