methyl 3,4,6-tri-O-benzyl-α-D-glucopyranosyl-(1->3)-2,4,6-tri-O-benzyl-α-D-glucopyranosyl-(1->3)-2-O-benzyl-(R)-4,6-O-benzylidene-α-D-mannopyranoside | 502181-63-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 3,4,6-tri-O-benzyl-α-D-glucopyranosyl-(1->3)-2,4,6-tri-O-benzyl-α-D-glucopyranosyl-(1->3)-2-O-benzyl-(R)-4,6-O-benzylidene-α-D-mannopyranoside
• 英文别名: methyl (3,4,6-tri-O-benzyl-α-D-glucopyranosyl)-(1-3)-(2,4,6-tri-O-benzyl-α-D-glucopyranosyl)-(1-3)-2-O-benzyl-(R)-4,6-O-benzylidene-α-D-mannopyranoside；(2R,3R,4R,5R,6R)-2-[(2R,3R,4S,5R,6R)-2-[[(2R,4aR,6S,7S,8S,8aR)-6-methoxy-2-phenyl-7-phenylmethoxy-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-8-yl]oxy]-3,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-4-yl]oxy-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-3-ol
• CAS: 502181-63-7
• 化学式: C₇₅H₈₀O₁₆
• 分子量: 1237.45
• InChiKey: QOMQXIJZQKWYIT-QBERRZBFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.8
• 重原子数：
  91
• 可旋转键数：
  29
• 环数：
  12.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  159
• 氢给体数：
  1
• 氢受体数：
  16

反应信息

• 作为反应物：
  描述：

  2-O-prop-1'-enyl-3,4,6-tri-O-benzyl-β-D-glucopyranosyl fluoride 、 methyl 3,4,6-tri-O-benzyl-α-D-glucopyranosyl-(1->3)-2,4,6-tri-O-benzyl-α-D-glucopyranosyl-(1->3)-2-O-benzyl-(R)-4,6-O-benzylidene-α-D-mannopyranoside 在 4 A molecular sieve 2,6-二叔丁基-4-甲基吡啶 、 碘 、 silver trifluoromethanesulfonate 作用下， 以 二氯甲烷 为溶剂， 以78%的产率得到methyl 3,4,6-tri-O-benzyl-2-O-(2-iodo-1-(3,4,6-tri-O-benzyl-1-deoxy-1-fluoro-β-D-glucopyranos-2-O-yl)propyl)-α-D-glucopyranosyl-(1->3)-2,4,6-tri-O-benzyl-α-D-glucopyranosyl-(1->3)-2-O-benzyl-4,6-O-benzylidene-α-D-mannopyranoside
  参考文献：
  名称：

  Allyl protecting group mediated intramolecular aglycon delivery: optimisation of mixed acetal formation and mechanistic investigation

  摘要：

  An efficient protocol for the formation of alpha-iodo mixed acetals, the first step of allyl-mediated 1AD, by reaction of allyl-derived enol ethers and alcohols, using I-2, AgOTf and di-tert-butyl methylpyridine as a novel source of I+, is reported. This reagent combination is capable of tethering glycosyl donors to the secondary alcohol groups of a variety of glycosyl acceptors including mono-, di- and trisaccharides. Mechanistic studies confirm the intramolecular nature of the glycosylation reaction, whilst the attempted use of diol glycosyl acceptors reveals limitations of both regio- and stereo selectivity in the glycosylation step. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2004.09.003
• 作为产物：
  描述：

  甲基-D-丙噻 在 N-碘代丁二酰亚胺 、 4 A molecular sieve 、 camphor-10-sulfonic acid 、 silver trifluoromethanesulfonate 、 二异丁基氢化铝 、 三氟甲烷磺酸甲酯 作用下， 以 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 24.08h， 生成 methyl 3,4,6-tri-O-benzyl-α-D-glucopyranosyl-(1->3)-2,4,6-tri-O-benzyl-α-D-glucopyranosyl-(1->3)-2-O-benzyl-(R)-4,6-O-benzylidene-α-D-mannopyranoside
  参考文献：
  名称：

  Total synthesis of the Glc3Man N-glycan tetrasaccharide

  摘要：

  The total synthesis of the tetrasaccharide Glcalpha(1-->2)Glcalpha(1-->3)Glcalpha(1-->3)ManalphaOMe, which corresponds to the terminal tetrasaccharide portion of the glucose terminated arm of the N-glycan tetradecasaccharide, was achieved by the use of differentially protected selenoglycosides and thioglycosides as glycosyl donors, all of which possessed non-participating protection of the 2-hydroxyl group. Favourable anomeric stereoselectivity was achieved for the glycosylation reactions by the use of ether as solvent, or co-solvent. Global deprotection by catalytic hydrogenation with palladium acetate in a mixture of ethanol and acetic acid yielded the target tetrasaccharide. (C) 2002 Published by Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4020(02)01221-8

文献信息

• Synthesis of the Glc3Man N-glycan tetrasaccharide by iterative allyl IAD
  作者：Emanuele Attolino、Ian Cumpstey、Antony J. Fairbanks

  DOI：10.1016/j.carres.2006.02.022

  日期：2006.7

  The synthesis of the tetrasaccharide alpha-D-Glcp-(1 -> 2)-alpha-D-Glcp-(1 -> 3)-alpha-D-Glcp-(1 -> 3)-alpha-D-Manp-OMe, corresponding to the terminal tetrasaccharide portion of the glucose terminated arm of the N-glycan tetradecasaccharide, was achieved with complete stereocontrol by the use of iterative allyl protecting group mediated intramolecular aglycon delivery (allyl IAD) demonstrating the utility of intramolecular glycosylation for the stereocontrolled construction of multiple glycosidic linkages during the synthesis of an oligosaccharide. (c) 2006 Elsevier Ltd. All rights reserved.
• Total synthesis of the Glc3Man N-glycan tetrasaccharide
  作者：S.C Ennis、I Cumpstey、A.J Fairbanks、T.D Butters、M Mackeen、M.R Wormald

  DOI：10.1016/s0040-4020(02)01221-8

  日期：2002.11

  The total synthesis of the tetrasaccharide Glcalpha(1-->2)Glcalpha(1-->3)Glcalpha(1-->3)ManalphaOMe, which corresponds to the terminal tetrasaccharide portion of the glucose terminated arm of the N-glycan tetradecasaccharide, was achieved by the use of differentially protected selenoglycosides and thioglycosides as glycosyl donors, all of which possessed non-participating protection of the 2-hydroxyl group. Favourable anomeric stereoselectivity was achieved for the glycosylation reactions by the use of ether as solvent, or co-solvent. Global deprotection by catalytic hydrogenation with palladium acetate in a mixture of ethanol and acetic acid yielded the target tetrasaccharide. (C) 2002 Published by Elsevier Science Ltd.
• Allyl protecting group mediated intramolecular aglycon delivery: optimisation of mixed acetal formation and mechanistic investigation
  作者：Ian Cumpstey、Kampanart Chayajarus、Antony J. Fairbanks、Alison J. Redgrave、Christopher M.P. Seward

  DOI：10.1016/j.tetasy.2004.09.003

  日期：2004.10

  An efficient protocol for the formation of alpha-iodo mixed acetals, the first step of allyl-mediated 1AD, by reaction of allyl-derived enol ethers and alcohols, using I-2, AgOTf and di-tert-butyl methylpyridine as a novel source of I+, is reported. This reagent combination is capable of tethering glycosyl donors to the secondary alcohol groups of a variety of glycosyl acceptors including mono-, di- and trisaccharides. Mechanistic studies confirm the intramolecular nature of the glycosylation reaction, whilst the attempted use of diol glycosyl acceptors reveals limitations of both regio- and stereo selectivity in the glycosylation step. (C) 2004 Elsevier Ltd. All rights reserved.