2-azido-3,4,6-tri-O-benzyl-2-deoxy-β-D-glucopyranosyl N,N,N',N'-tetramethylphosphorodiamidate

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-azido-3,4,6-tri-O-benzyl-2-deoxy-β-D-glucopyranosyl N,N,N',N'-tetramethylphosphorodiamidate
• 英文别名: N-[[(2S,3R,4R,5S,6R)-3-azido-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-yl]oxy-(dimethylamino)-oxidophosphaniumyl]-N-methylmethanamine
• 化学式: C₃₁H₄₀N₅O₆P
• 分子量: 609.662
• InChiKey: SPBYTEFVGDTWNV-CWMPKMHISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  43
• 可旋转键数：
  15
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  90
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为产物：
  描述：

  双(二甲胺基)氯酸磷 、 2-azido-3,4,6-tri-O-benzyl-2-deoxy-D-glucopyranose 在 六甲基磷酰三胺 、 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.5h， 生成 2-azido-3,4,6-tri-O-benzyl-2-deoxy-α-D-glucopyranosyl N,N,N',N'-tetramethylphosphorodiamidate 、 2-azido-3,4,6-tri-O-benzyl-2-deoxy-β-D-glucopyranosyl N,N,N',N'-tetramethylphosphorodiamidate
  参考文献：
  名称：

  A highly stereoselective construction of 1,2-trans-β-glycosidic linkages capitalizing on 2-azido-2-deoxy-d-glycosyl diphenyl phosphates as glycosyl donors

  摘要：

  The scope of TMSOTf-promoted glycosidation of 2-azido-2-deoxyglycopyranosyl diphenyl phosphates is investigated. The 3,4,6-tri-O-benzyl-protected glucosyl and galactosyl donors and the 4,6-O-benzylidene-protected galactosyl donor each react with a range of acceptor alcohols in the presence of a stoichiometric amount of TMSOTf in propionitrile at -78 degreesC to afford 1,2-trans-beta-linked disaccharides in high yields with alpha:beta ratios ranging from 9:91 to 1: > 99, regardless of the anomeric composition of the donor used. The use of propionitrile as a solvent at -78 degreesC has proven to be among the best choice for the highest levels of beta-selectivity reported to date for this type of glycosidation. A plausible reaction mechanism, which features a large equilibrium preference for alpha-glycosyl-nitrilium ions over beta-nitrilium ions, is proposed based on byproducts formed through their intermediacy and accounts for the observed excellent beta-selectivities. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2004.08.076

文献信息

• A highly stereoselective construction of 1,2-trans-β-glycosidic linkages capitalizing on 2-azido-2-deoxy-d-glycosyl diphenyl phosphates as glycosyl donors
  作者：Toshifumi Tsuda、Seiichi Nakamura、Shunichi Hashimoto

  DOI：10.1016/j.tet.2004.08.076

  日期：2004.11

  The scope of TMSOTf-promoted glycosidation of 2-azido-2-deoxyglycopyranosyl diphenyl phosphates is investigated. The 3,4,6-tri-O-benzyl-protected glucosyl and galactosyl donors and the 4,6-O-benzylidene-protected galactosyl donor each react with a range of acceptor alcohols in the presence of a stoichiometric amount of TMSOTf in propionitrile at -78 degreesC to afford 1,2-trans-beta-linked disaccharides in high yields with alpha:beta ratios ranging from 9:91 to 1: > 99, regardless of the anomeric composition of the donor used. The use of propionitrile as a solvent at -78 degreesC has proven to be among the best choice for the highest levels of beta-selectivity reported to date for this type of glycosidation. A plausible reaction mechanism, which features a large equilibrium preference for alpha-glycosyl-nitrilium ions over beta-nitrilium ions, is proposed based on byproducts formed through their intermediacy and accounts for the observed excellent beta-selectivities. (C) 2004 Elsevier Ltd. All rights reserved.