Premium
The Oxidation of S ‐Acetyl by Nitrite: Mechanism and Application
Author(s) -
Ge JianTao,
Zhang LeFeng,
Pu Liang,
Zhang Ying,
Pei ZhiChao,
Dong Hai
Publication year - 2020
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.202003566
Subject(s) - nitrite , chemistry , nitrosylation , nitrosation , oxide , medicinal chemistry , acetylation , glycosyl , reaction mechanism , organic chemistry , polymer chemistry , nitric oxide , catalysis , nitrate , biochemistry , gene
Abstract Straightforward S‐S bond formation via the oxidation of S ‐acetyl group by nitrite was observed and the mechanism was explored in this study. The observed reaction was found to be initiated via a S ‐nitrosylation followed by the S‐S bond formation that accompanies nitrite oxide (NO) release. The reaction approach was further analyzed by quantum chemical studies, surpporting a mechanism of first generating nitrous ester. Unlike S ‐nitrosylation between thiols and nitrite proceeding at a strong alkaline condition due to the formation of hydroxyl anion, the S ‐nitrosylation between S ‐acetyl and nitrite proceed at a condition close to neutrality due to the formation of acetate instead. Using this reaction, per‐ O ‐acetylated glycosyl disulfides were obtained in high yields at mild condition. Furthermore, per‐ O ‐acetylated glycosyl 1‐thiols were also efficiently prepared starting from per‐acetylated 1‐thio‐glycoses in a one‐pot reaction including the oxidation of S ‐acetyl group by nitrite and the reduction of disulfides.