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

被引：57

作者：

Kashiwagi, Y

Kurashima, F

Kikuchi, C

Anzai, J

Osa, T

Bobbitt, JM

机构：

[1] Tohoku Univ, Grad Sch Pharmaceut Sci, Aoba Ku, Sendai, Miyagi 9808578, Japan

[2] Univ Connecticut, Dept Chem, Storrs, CT 06269 USA

来源：

TETRAHEDRON LETTERS | 1999年 / 40卷 / 35期

关键词：

electrochemical reactions; nitoxides; enantiomeric purity; resolution;

D O I：

10.1016/S0040-4039(99)01325-8

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

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 sar-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. (C) 1999 Elsevier Science Ltd. All rights reserved.

引用

页码：6469 / 6472

页数：4

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