153081-98-2

Upstream product

• 1092103-60-0 1,5-anhydro-3,4,6-tri-O-benzyl-2-deoxy-2-C-methoxymethyl-D-lyxo-hex-1-enitol 
• 67-56-1 methanol 
• 153496-00-5 1,5-anhydro-3,4,6-tri-O-benzyl-2-deoxy-2-hydroxymethyl-D-lyxo-hex-1-enitol 
• 136982-88-2 (2R,3R,4R)-3,4-bis(benzyloxy)-2-((benzyloxy)methyl)-3,4-dihydro-2H-pyran-5-carbaldehyde 
• 153081-97-1 3,4,6-tri-O-benzyl-2-C-acetoxymethylgalactal 

Downstream Products

• 218445-42-2 methyl 3,4,6-tri-O-benzyl-2-deoxy-2-C-methyl-α-D-talohexopyranoside 

Relevant academic research and scientific papers

Stereoselective synthesis of 2-C-methylene glycosides and disaccharides via direct allylic substitution of hydroxy group in benzylated glycals

InCl3 efficiently catalyzes allylic substitution of the hydroxy group of 2-C-hydroxymethyl glycals to afford a diversity of 2-C-methylene alkyl and aryl glycosides as well as disaccharides in high yields. This protocol surpasses the existing methods for the synthesis of 2-C-methylene glycosides as it obviates the need for functionalizing the allylic hydroxy group of glycals. The interest of this methodology relies on the extremely mild conditions required even with a free hydroxyl group at the allylic position of the glycals and that too only with a catalytic amount of InCl3. The reaction is fast (30 min.), stereoselective and is compatible with a variety of oxygenated nucleophiles including those possessing acid-labile groups. A mechanistic investigation on the direct formation of an α,α-(1→1)linked disaccharide derivative from 2-C-hydroxymethyl galactal reveals that the reaction proceeds through a domino Ferrier rearrangement followed by a facile 1,3-alkoxy migration.

InCl3-catalyzed rapid 1,3-alkoxy migration in glycal ethers: Stereoselective synthesis of unsaturated α-O-glycosides and an α,α-(1→1)-linked disaccharide

InCl3 catalyzes a facile stereoselective 1,3-migration of allylic ethers of glycals to afford 2-C-methylene- and 2,3-unsaturated-α- O-glycosides in high yields. The reaction is rapid (10 min), requires only 20 mol-% of the catalyst, and is compatible with acid-labile functional groups such as epoxides and acetals. This methodology provides a convenient alternative to the Ferrier rearrangement. A direct synthesis of an α,α-(1→1)- linked disaccharide derivative by a domino process is also reported. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

A New Ferrier System: 2-C-Acetoxymethylglycals. A Convenient Entry to 2-C-Methylene Glycosides

Synthesis of tri-O-benzyl-2-C-acetoxymethylglycals and subsequent Ferrier rearrangement to give 2-C-methylene glycosides is described.