319922-17-3

Upstream product

• 4163-65-9 per-O-acetyl-α-D-mannopyranose 
• 28541-75-5 p-methoxyphenyl α-D-mannopyranoside 
• 106-95-6 allyl bromide 
• 150-76-5 4-methoxy-phenol 
• 17042-40-9 4-methoxyphenyl 2,3,4,6-tetra-O-acetyl-1-α-D-mannopyranoside 

Downstream Products

• 1002744-65-1 p-methoxyphenyl 3-O-allyl-2,4,6-tri-O-benzyl-α-D-mannopyranoside 
• 319922-26-4 2,2,2-Trichloro-acetimidic acid (2R,4aR,6R,7S,8S,8aR)-8-allyloxy-7-benzyloxy-2-phenyl-hexahydro-pyrano[3,2-d][1,3]dioxin-6-yl ester 
• 319922-22-0 4-methoxyphenyl 3-O-allyl-2-O-benzyl-4,6-O-benzylidene-α-D-mannopyranoside 
• 431981-82-7 methyl 3-O-allyl-2,4,6-tri-O-benzoyl-α-D-mannopyranosyl-(1->3)-2-O-benzoyl-4,6-O-benzylidene-α-D-mannopyranoside 
• 431981-83-8 methyl 3-O-allyl-2,4,6-tri-O-benzoyl-α-D-mannopyranosyl-(1->3)-2-O-benzoyl-α-D-mannopyranoside 
• 431981-81-6 methyl 3-O-allyl-2,4,6-tri-O-benzoyl-α-D-mannopyranosyl-(1->3)-4,6-O-benzylidene-α-D-mannopyranoside 
• 500217-09-4 2,3,4,6-tetra-O-benzoyl-α-D-mannopyranosyl-(1-> 3)-2,4,6-tri-O-benzoyl-α-D-mannopyranosyl trichloroacetimidate 
• 500217-05-0 p-methoxyphenyl 2,3,4,6-tetra-O-benzoyl-α-D-mannopyranosyl-(1->3)-2,4,6-tri-O-benzoyl-α-D-mannopyranoside 
• 500217-14-1 3-O-allyl-2,4,6-tri-O-benzoyl-α-D-mannopyranosyl-(1-3)-2,4,6-tri-O-benzoyl-α-D-mannopyranosyl trichloroacetimidate 
• 500217-11-8 p-methoxyphenyl 3-O-allyl-2,4,6-tri-O-benzoyl-α-D-mannopyranosyl-(1-3)-2,4,6-tri-O-benzoyl-α-D-mannopyranoside 
• 500217-07-2 3-O-(2,3,4,6-tetra-O-benzoyl-α-D-mannopyranosyl)-2,4,6-tri-O-benzoyl-α-D-mannopyranose 
• 500217-12-9 p-methoxyphenyl 2,4,6-tri-O-benzoyl-α-D-mannopyranosyl-(1-3)-2,4,6-tri-O-benzoyl-α-D-mannopyranoside 
• 500217-13-0 C₅₇H₅₀O₁₇ 
• 431981-80-5 3-O-allyl-2,4,6-tri-O-benzoyl-α-D-mannopyranoside trichloroacetimidate 

Relevant academic research and scientific papers

Synthesis of the 'primer-adaptor' trisaccharide moiety of Escherichia coli O8, O9, and O9a lipopolysaccharide

Described is the synthesis of the trisaccharide α-d-Manp-(1→3)-α-d-Manp-(1→3)-β-d-GlcpNAcO(CH 2)8N3, the glycan portion of which corresponds to the 'adaptor-primer' moiety linking the O-chain and core oligosaccharide in th

Synthesis of α-Manp-(1→2)-α-Manp-(1→3)-α-Manp-(1→3)-Manp, the tetrasaccharide repeating unit of Escherichia coli O9a, and α-Manp-(1→2)-α-Manp-(1→2)-α-Manp-(1→3)- α-Manp-(1→3)-Manp, the pentasaccharide repeating unit of E. coli O9 and Klebsiella O3

The tetrasaccharide repeating unit of Escherichia coli O9a, α-D-Manp-(1→2)-α-D-Manp-(1→3)-α-D-Manp- (1→3)-D-Manp, and the pentasaccharide repeating unit of E. coli O9 and Klebsiella O3, α-D-Manp-(1→2)-α-D-Manp-(1→2)-α-D-Manp- (1→3)-α-D-Manp-(1→3)-D-Manp, were synthesized as their methyl glycosides. Thus, selective 3-O-allylation of p-methoxyphenyl α-D-mannopyranoside via a dibutyltin intermediate gave p-methoxyphenyl 3-O-allyl-α-D-mannopyranoside (2) in good yield. Benzoylation (→3), then removal of 1-O-methoxyphenyl (→4), and subsequent trichloroacetimidation afforded the 3-O-allyl-2,4,6-tri-O-benzoyl-α-D-mannopyranosyl trichloroacetimidate (5). Condensation of 5 with methyl 4,6-O-benzylidene-α-D-mannopyranoside (6) selectively afforded the (1→3)-linked disaccharide 7. Benzoylation of 7, debenzylidenation, benzoylation, and deallylation gave methyl 2,4,6-tri-O-benzoyl-α-D-mannopyranosyl-(1→3)-2,4,6-tri-O-benzoyl- α-D-mannopyranoside (11) as the disaccharide acceptor. Coupling of 11 with (1→2)-linked mannose disaccharide donor 17 or trisaccharide donor 21, followed by deacylation, furnished the target tetrasaccharide and pentasaccharide, respectively.

An efficient and practical synthesis of α-(1→3)-linked mannohexaose and mannooctaose

α-(1→3)-Linked mannohexaose and mannooctaose as their methyl glycosides were synthesized from condensation of the corresponding α-(1→3)-linked di- (9) and tetrasaccharide donor (21) with the tetrasaccharide acceptor (23), respectively, followed by deacylation. The donor 21 and acceptor 23 were prepared readily from activation of C-1 of the tetrasaccharide 20 and deallylation of the tetrasaccharide 22, respectively. The tetrasaccharide 20 was prepared from oxidative cleavage of 1-O-p-methoxyphenyl of 19, which was obtained from coupling of 9 with 11. The tetrasaccharide 22 was obtained from condensation of the donor 13 with the acceptor 18. These disaccharides 9, 11, 13, and 18 were produced easily by simple chemical transformation using p-methoxyphenyl 3-O-allyl-α-D-mannopyranoside (1) and 2,3,4,6-tetra-O-benzoyl-α-D-mannopyranosyl trichloroacetimidate (6), and methyl 3-O-allyl-α-D-mannopyranoside (14) as the synthons.

Can preferential β-mannopyranoside formation with 4,6-O-benzylidene protected mannopyranosyl sulfoxides be reached with trichloroacetimidates?

Studies with 3-O-allyl-2-O-benzyl-4,6-O-benzylidene-α-D-mannopyranosyl sulfoxide (3d) and the corresponding trichloroacetimidate (4) as glycosyl donors and various acceptors (A-F) led under similar reaction conditions to similar glycosylation results, i.e. mainly or exclusively the β-anomers of glycosides 5dA-5dF could be obtained. Thus, the versatile building block 5dA for N-glycan synthesis is readily available. For the activation of the sulfoxide leaving group, one equivalent of Tf2O and two equivalents of DTBMP are required, whereas for trichloroacetimidate activation catalytic amounts of TMSOTf are sufficient; hence, the trichloroacetimidate based procedure is very convenient. Various parameters were modified in the reaction of 4 with A (catalyst concentration, configuration of 4, size of the 2-O-protective group, solvent), thus, a proposal for the reaction course was derived. (C) 2000 Elsevier Science Ltd.