A new synthesis of 6-O-acylsucroses and of mixed 6,6'-di-O-acylsucroses.
Various 6-O-acylsucroses were synthesized in good yields from unprotected sucrose in N,N-dimethylformamide and the appropriate 3-acylthiazolidine-2-thiones 6 or 3-acyl-5-methyl-1,3,4-thiadiazole-2(3H)-thiones 7. A selective ionization of the free sugar by sodium hydride or triethylamine, followed by acylation with 6, gave 2-O-acylsucroses which were subjected in situ to intramolecular isomerizations using 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or an aqueous solution of triethylamine to yield 6-O-acylsucroses. The later were otherwise obtained directly when sucrose was acylated with 6 or 7 in the presence of DBU. Moreover, mixed 6,6'-di-O-acylsucroses were readily obtained from 6'-monoacylates by using a Mitsunobu reaction without involving the concomitant formation of the 3',4'-epoxide.
Baczko
K
K
Laboratoire de Synthèses et Activations de Biomolécules, associé au CNRS, Ecole Nationale Supérieure de Chimie, Rennes, France.
Nugier-Chauvin
C
C
Banoub
J
J
Thibault
P
P
Plusquellec
D
D
D000215:Acylation; D002240:Carbohydrate Sequence; D004187:Disaccharides / Q000138:chemical synthesis* / Q000737:chemistry; D008969:Molecular Sequence Data; D013395:Sucrose / Q000737:chemistry* / Q000378:metabolism
D004187:Disaccharides; D013395:Sucrose