Significant substituent effect on the anomerization of pyranosides: mechanism of anomerization and synthesis of a 1,2-cis glucosamine oligomer from the 1,2-trans anomer.
Chemistry
; 20(1): 124-32, 2014 Jan 03.
Article
em En
| MEDLINE
| ID: mdl-24307501
ABSTRACT
Aminoglycosides containing a 2,3-trans carbamate group easily undergo anomerization from the 1,2-trans glycoside to the 1,2-cis isomer under mild acidic conditions. The N-substituent of the carbamate has a significant effect on the anomerization reaction; in particular, an N-acetyl group facilitated rapid and complete α-anomerization. The differences in reactivity due to the various N-substituents were supported by the results of DFT calculations; the orientation of the acetyl carbonyl group close to the anomeric position was found to contribute significantly to the directing of the anomerization reaction. By exploiting this reaction, oligoaminoglycosides with multiple 1,2-cis glycosidic bonds were generated from 1,2-trans glycosides in a one-step process.
Palavras-chave
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Assunto principal:
Glucosamina
/
Aminoglicosídeos
Idioma:
En
Revista:
Chemistry
Assunto da revista:
QUIMICA
Ano de publicação:
2014
Tipo de documento:
Article