922183-00-4

Upstream product

• 18162-48-6 tert-butyldimethylsilyl chloride 
• 159407-19-9 phenyl 4,6-O-benzylidene-1-thio-α-D-mannopyranoside 
• 13992-16-0 phenyl 2,3,4,6-tetra-O-acetyl-1-thio-α-D-mannopyranoside 
• 2936-70-1 (2R,3S,4S,5S,6R)-2-Hydroxymethyl-6-phenylsulfanyl-tetrahydro-pyran-3,4,5-triol 
• 108-98-5 thiophenol 
• 530-26-7 D-Mannose 
• 69739-34-0 t-butyldimethylsiyl triflate 

Downstream Products

• 1607005-93-5 phenyl 4-O-benzyl-3-O-tert-butyldimethylsilyl-6-cyano-2-O-(2-naphthylmethyl)-1-thio-α-D-mannopyranoside 
• 1607005-95-7 phenyl 4-O-benzyl-3-O-tert-butyldimethylsilyl-6-deoxy-2-O-(2-naphthylmethyl)-1-thio-α-D-manno-heptopyranoside 
• 1607006-38-1 C₃₈H₃₈O₅S 
• 1607006-01-8 phenyl 4,7-di-O-benzyl-3-O-tert-butyldimethylsilyl-6-deoxy-2-O-(2-naphthylmethyl)-1-thio-α-D-manno-heptopyranoside 
• 1607006-14-3 (5-amino-N-benzyloxycarbonyl-1-pentyl) 4,7-Di-O-benzyl-3-O-tert-butyldimethylsilyl-6-deoxy-β-D-manno-heptopyranoside 
• 1607005-86-6 phenyl 4-O-benzyl-3-O-tert-butyldimethylsilyl-2-O-(2-naphthylmethyl)-1-thio-α-D-mannopyranoside 
• 1607006-36-9 C₃₀H₃₀O₅S 
• 1607005-89-9 phenyl 3,6-anhydro-4-O-benzyl-2-O-(2-naphthylmethyl)-1-thio-α-D-mannopyranoside 
• 1607005-97-9 C₃₇H₄₄O₅SSi 
• 1607005-90-2 phenyl 4-O-benzyl-3-O-tert-butyldimethylsilyl-2-O-(2-naphthylmethyl)-1-thio-6-O-tosyl-α-D-mannopyranoside 
• 1250346-19-0 phenyl 4,6-O-benzylidene-3-O-tert-butyldimethylsilyl-2-O-(2-naphthylmethyl)-1-thio-α-D-mannopyranoside 
• 1441884-93-0 C₃₃H₄₈O₁₂Si 

Relevant academic research and scientific papers

Total Synthesis of Tiacumicin B: Implementing Hydrogen Bond Directed Acceptor Delivery for Highly Selective β-Glycosylations

A total synthesis of tiacumicin B, a natural macrolide whose remarkable antibiotic properties are used to treat severe intestinal infections, is reported. The strategy is in part based on the prior synthesis of the tiacumicin B aglycone, and on the decisive use of sulfoxides as anomeric leaving groups in hydrogen-bond-mediated aglycone delivery (HAD). This new HAD variant permitted highly β-selective rhamnosylation and noviosylation. To increase convergence, the rhamnosylated C1–C3 fragment thus obtained was anchored to the C4–C19 aglycone fragment by adapting the Suzuki–Miyaura cross-coupling used for the aglycone synthesis. Ring-size-selective macrolactonization provided a compound engaged directly in the noviolysation step with virtually total β selectivity. The final efficient removal of all the protecting groups provided synthetic tiacumicin B.

Intramolecular aglycon delivery enables the synthesis of 6-deoxy-β-d-manno-heptosides as fragments of Burkholderia pseudomallei and Burkholderia mallei capsular polysaccharide

Burkholderia pseudomallei and Burkholderia mallei are potential bioterrorism agents. They express the same capsular polysaccharide (CPS), a homopolymer featuring an unusual [→3)-2-O-acetyl-6-deoxy-β-d-manno- heptopyranosyl-(1→] as the repeating unit. This CPS is known to be one of the main targets of the adaptive immune response in humans and therefore represents a crucial subunit candidate for vaccine development. Herein, the stereoselective synthesis of mono- and disaccharidic fragments of the B. pseudomallei and B. mallei CPS repeating unit is reported. The synthesis of 6-deoxy-β-d-manno-heptosides was investigated using both inter- and intramolecular glycosylation strategies from thio-manno-heptose that was modified with 2-naphthylmethyl (NAP) at C2. We show here that NAP-mediated intramolecular aglycon delivery (IAD) represents a suitable approach for the stereocontrolled synthesis of 6-deoxy-β-d-manno-heptosides without the need for rigid 4,6-O-cyclic protection of the sugar skeleton. The IAD strategy is highly modular, as it can be applied to structurally diverse acceptors with complete control of stereoselectivity. Problematic hydrogenation of the acetylated disaccharides was overcome by using a microfluidic continuous flow reactor.

Carbene-mediated functionalization of the anomeric C-H bond of carbohydrates: Scope and limitations

Herein we investigate the scope and limitations of a new synthetic approach towards α- and β-ketopyranosides relying on the functionalization of the anomeric C-H bond of carbohydrates by insertion of a metal carbene. A key bromoacetate grafted at the 2-position is the cornerstone of a stereoselective glycosylation/diazotransfer/quaternarization sequence that makes possible the construction of a quaternary center with complete control of the stereochemistry. This sequence shows a good tolerance toward protecting groups commonly used in carbohydrate chemistry and gives rise to quaternary disaccharides with good efficiency. In the case of a disaccharide with a more restricted conformation, this functionalization process can be hampered by the steric demand next to the targeted anomeric position. In addition, the formation of transient orthoesters during the glycosylation step may also reduce the overall efficiency of the synthetic sequence. Copyright

Dialkylphosphates as stereodirecting protecting groups in oligosaccharide synthesis

(Chemical Equation Presented) Double duty: A phosphoric ester at the C2 position in glycosyl donors directs the glycosylation to occur selectively at the anomeric carbon atom with complete 1,2-trans selectivity. Since the phosphoric ester can be removed to give the hydroxy function, this group serves as a stereodirecting protecting group in oligosaccharide synthesis.