153082-00-9

Upstream product

• 67-56-1 methanol 
• 153153-30-1 2-acetoxymethyl-1,5-anhydro-3,4,6-tri-O-benzyl-2-deoxy-D-arabino-hex-1-enitol 
• 1003194-59-9 C₃₁H₃₂O₅ 
• 136883-91-5 (2R,3S,4R)-3,4-bis(benzyloxy)-2-((benzyloxy)methyl)-3,4-dihydro-2H-pyran-5-carbaldehyde 
• 153547-53-6 1,5-anhydro-3,4,6-tri-O-benzyl-2-deoxy-2-hydroxymethyl-D-arabino-hex-1-enitol 
• 1207164-10-0 methyl (2E)-3,4,6-tri-O-benzyl-2-C-(bromomethylene)-2-deoxy-α-D-arabino-hexopyranoside 
• 1092103-66-6 1,5-anhydro-3,4,6-tri-O-benzyl-2-deoxy-2-C-methoxymethyl-D-arabino-hex-1-enitol 

Relevant academic research and scientific papers

Divergent synthesis of 2-C-branched pyranosides and oxepines from 1,2-gem-dibromocyclopropyl carbohydrates

The ring opening of 1,2-(gem-dibromo)cyclopropyl carbohydrates by two different modes leads to either 2-C-(bromomethylene)pyranosides (using base) or 2-bromooxepines (using silver salts), as shown previously by us for a D-glucal-derived cyclopropane. The base-promoted ring opening is extended to encompass additional alcohol, thiol and amine nucleophiles, and diastereoisomeric cyclopropane precursors. Cross-coupling of the 2-C-(bromomethylene)pyranosides leads to extended 2-C-branched pyranosides. Silver-promoted ring expansion of the cyclopropyl carbohydrates in the presence of various alcohols is described. Cross-coupling of the resulting benzyl 2-bromooxepines affords 2-C-substituted oxepines.

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.

Synthesis of oxepines and 2-branched pyranosides from a D-glucal-derived gem-dibromo-1,2-cyclopropanated sugar

(Chemical Equation Presented) The conversion of cyclopropane-fused carbohydrates into oxepines is an attractive method for accessing diverse members of the septanoside family of carbohydrate mimetics. 2-Bromooxepines are obtained through silver(I)-promoted thermal ring expansion of a D-glucal-derived gem-dihalocyclopropanated sugar. In contrast, cyclopropane ring cleavage under basic conditions leads to 2-C-branched pyranosides, not the 2-bromooxepine structures assigned in an earlier report.

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.

Synthesis of C-2 methylene glycosides from C-2 propargyloxymethyl glycals exploiting the alkynophilicity of AuCl3

C-2 Methylene glycosides were synthesized from C-2 propargyloxymethyl glycals in a stereoselective manner using a catalytic quantity of AuCl3. The Au-catalyzed reaction was explored using various aglycones. The current protocol enables the prep

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.