DAST-mediated regioselective anomeric group migration in saccharides.
When saccharides bearing a sulfur, selenium, or oxygen substituent at the anomeric center and an unprotected hydroxyl group either at C-4 or C-6 were subjected to fluorination with DAST in dichloromethane, a regioselective migration of the anomeric substituent to the C-4 or C-6 position was observed. Certain saccharides gave a mixture of migration and normal fluorination products whereas others yielded mainly or exclusively migration products (beta-glycosyl fluorides). The high thermal and chemical stability of migrated glycosyl fluorides were demonstrated to be an important precursor for many significant carbohydrate analogies. It is therefore suggested that these migrations may have useful applications in organic synthesis.
Lin
Po-Chiao
PC
Department of Chemistry, National Tsing Hua University, Hsichu-300, Taiwan.
Adak
Avijit Kumar
AK
Ueng
Shau-Hua
SH
Huang
Li-De
LD
Huang
Kuo-Ting
KT
Ho
Ja-an Annie
JA
Lin
Chun-Cheng
CC
D002241:Carbohydrates / Q000737:chemistry*; D004048:Diethylamines / Q000737:chemistry; D005461:Fluorine / Q000737:chemistry; D054879:Halogenation; D055601:Organic Chemistry Phenomena; D013237:Stereoisomerism
D002241:Carbohydrates; D004048:Diethylamines; D005461:Fluorine; C040394:diethylaminosulfur trifluoride