Divergent synthesis of L-sugars and L-iminosugars from D-sugars.
An efficient divergent synthesis of L-sugars and L-iminosugars from D-sugars is described. The important intermediate, delta-hydroxyalkoxamate, prepared from D-glucono-/galactono-1,5-lactone, was cyclized under Mitsunobu conditions to give the O-cyclized oxime compound and the N-cyclized lactam compound as mixtures. A more detailed investigation revealed that the appropriate protecting groups and solvents controlled the specificity for the O-/N-cyclization of the delta-hydroxyalkoxamate. Suitable protection at the 6-position of delta-hydroxyalkoxamate, derived from D-glucono-1,5-lactone, afforded the corresponding O-alkylation product alone. Thus we succeeded in applying this to the total synthesis of L-iduronic acid. In contrast, with both TBDMS as the protecting group and RCN as the solvent the efficient conversion of D-glucono/galactono-1,5-lactone into the corresponding L-iminosugars (L-idonolactam and L-altronolactam) was achieved.
Takahashi
Hideyo
H
School of Pharmaceutical Sciences, Teikyo University, Sagamiko, Sagamihara, Kanagawa, 199-0195, Japan.
Shida
Tomomi
T
Hitomi
Yuko
Y
Iwai
Yoshinori
Y
Miyama
Namisa
N
Nishiyama
Kazusa
K
Sawada
Daisuke
D
Ikegami
Shiro
S
D002236:Carbohydrate Conformation; D002241:Carbohydrates / Q000138:chemical synthesis* / Q000737:chemistry; D003500:Cyclization; D007067:Iduronic Acid / Q000138:chemical synthesis*; D050111:Imino Sugars / Q000138:chemical synthesis*; D007783:Lactones / Q000737:chemistry; D012833:Siloxanes / Q000737:chemistry; D013343:Styrenes / Q000737:chemistry
C506477:4-(tert-butyldimethylsiloxy)styrene; D002241:Carbohydrates; D050111:Imino Sugars; D007783:Lactones; D012833:Siloxanes; D013343:Styrenes; D007067:Iduronic Acid