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

Yoshitomo Kashiwagi; Futoshi Kurashima; Chikara Kikuchi; Jun ichi Anzai; Tetsuo Osa; James M. Bobbitt

doi:10.1016/S0040-4039(99)01325-8

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

Yoshitomo Kashiwagi, Futoshi Kurashima, Chikara Kikuchi, Jun ichi Anzai, Tetsuo Osa, James M. Bobbitt

Research output: Contribution to journal › Article › peer-review

60 Citations (Scopus)

Abstract

Nitroxyl radical (6S,7R,10R)-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.

Original language	English
Pages (from-to)	6469-6472
Number of pages	4
Journal	Tetrahedron Letters
Volume	40
Issue number	35
DOIs	https://doi.org/10.1016/S0040-4039(99)01325-8
Publication status	Published - 1999 Aug 27
Externally published	Yes

Keywords

Electrochemical reactions
Enantiomeric purity
Nitoxides
Resolution

ASJC Scopus subject areas

Biochemistry
Drug Discovery
Organic Chemistry

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10.1016/S0040-4039(99)01325-8

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@article{533bde84713f4e5d9cb42657bdf13fca,

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

abstract = "Nitroxyl radical (6S,7R,10R)-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.",

keywords = "Electrochemical reactions, Enantiomeric purity, Nitoxides, Resolution",

author = "Yoshitomo Kashiwagi and Futoshi Kurashima and Chikara Kikuchi and Anzai, {Jun ichi} and Tetsuo Osa and Bobbitt, {James M.}",

note = "Funding Information: Acknowledgments This work was supported in part by Grants-in-Aid for Scientific Research on Priority Areas (No. 10132206: ~Innovative Synthetic Reactions{"}) and for Encouragement Research (No. 10771266) from the Ministry of Education, Science, Sports and Culture of Japan.",

year = "1999",

month = aug,

day = "27",

doi = "10.1016/S0040-4039(99)01325-8",

language = "English",

volume = "40",

pages = "6469--6472",

journal = "Tetrahedron Letters",

issn = "0040-4039",

publisher = "Elsevier Limited",

number = "35",

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TY - JOUR

T1 - Enantioselective electrocatalytic oxidation of racemic sec-alcohols using a chiral 1-azaspiro[5.5]undecane-N-oxyl radical

AU - Kashiwagi, Yoshitomo

AU - Kurashima, Futoshi

AU - Kikuchi, Chikara

AU - Anzai, Jun ichi

AU - Osa, Tetsuo

AU - Bobbitt, James M.

N1 - Funding Information: Acknowledgments This work was supported in part by Grants-in-Aid for Scientific Research on Priority Areas (No. 10132206: ~Innovative Synthetic Reactions") and for Encouragement Research (No. 10771266) from the Ministry of Education, Science, Sports and Culture of Japan.

PY - 1999/8/27

Y1 - 1999/8/27

N2 - Nitroxyl radical (6S,7R,10R)-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.

AB - Nitroxyl radical (6S,7R,10R)-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.

KW - Electrochemical reactions

KW - Enantiomeric purity

KW - Nitoxides

KW - Resolution

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U2 - 10.1016/S0040-4039(99)01325-8

DO - 10.1016/S0040-4039(99)01325-8

M3 - Article

AN - SCOPUS:0033609758

SN - 0040-4039

VL - 40

SP - 6469

EP - 6472

JO - Tetrahedron Letters

JF - Tetrahedron Letters

IS - 35

ER -

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

Abstract

Keywords

ASJC Scopus subject areas

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