The stereoselective transformation of the cyclopropyl derivative 2, stereoselectively obtained with the Simmons–Smith reaction of methyl 2,6-di-O-benzyl-α-l-threo-hex-4-enopyranoside (1), into gabosines and deoxy-carbahexoses is described. The treatment of 2 with mercuric trifluoroacetate in dry methanol gives the organomercuric chloride 3, which by demercuration with lithium aluminum hydride affords the 4-C-deoxy-4-methyl-1,5-bis-glycoside 4. The acid hydrolysis of 4 produces a mixture of the two diastereoisomeric 2-methyl-cyclohex-2-enones 6 and 7, catalytically reduced to carba-sugars 10 and 11. Structures and stereochemistry of all isolated compounds were determined by 1D and 2D NMR experiments

A new Method for the Synthesis of Carba-sugars Enones (Gabosines) Using a Mercury(II)-Mediated Opening of 4,5-Cyclopropanated Pyranosides as the Key-step

CORSARO, Antonino;CHIACCHIO, MARIA ASSUNTA ROSSELLA;PISTARA', Venerando
2006-01-01

Abstract

The stereoselective transformation of the cyclopropyl derivative 2, stereoselectively obtained with the Simmons–Smith reaction of methyl 2,6-di-O-benzyl-α-l-threo-hex-4-enopyranoside (1), into gabosines and deoxy-carbahexoses is described. The treatment of 2 with mercuric trifluoroacetate in dry methanol gives the organomercuric chloride 3, which by demercuration with lithium aluminum hydride affords the 4-C-deoxy-4-methyl-1,5-bis-glycoside 4. The acid hydrolysis of 4 produces a mixture of the two diastereoisomeric 2-methyl-cyclohex-2-enones 6 and 7, catalytically reduced to carba-sugars 10 and 11. Structures and stereochemistry of all isolated compounds were determined by 1D and 2D NMR experiments
2006
4,5-cyclopropanated sugars; intramolecular aldol condensation; gabosines; 6-deoxy-5a-carba-hexopyranosides
File in questo prodotto:
File Dimensione Formato  
40) Tet Lett 2006, 47, 6591-6594.pdf

solo gestori archivio

Licenza: Non specificato
Dimensione 126.56 kB
Formato Adobe PDF
126.56 kB Adobe PDF   Visualizza/Apri

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/20.500.11769/9035
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 19
  • ???jsp.display-item.citation.isi??? 20
social impact