2,3,4,6-tetra-O-benzyl-β-D-mannopyranose 1-O-trichloroacetimidate | 103368-06-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,3,4,6-tetra-O-benzyl-β-D-mannopyranose 1-O-trichloroacetimidate
• 英文别名: Bn(-2)[Bn(-3)][Bn(-4)][Bn(-6)]Man(b)-O-C(NH)CCl3；[(2S,3S,4S,5R,6R)-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-yl] 2,2,2-trichloroethanimidate
• CAS: 103368-06-5
• 化学式: C₃₆H₃₆Cl₃NO₆
• 分子量: 685.044
• InChiKey: LMICALCPRSCSMO-ZOHVZMGWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.5
• 重原子数：
  46
• 可旋转键数：
  15
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  79.2
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2,3,4,6-tetra-O-benzyl-β-D-mannopyranose 1-O-trichloroacetimidate 在 N-溴代丁二酰亚胺(NBS) 、 三氟甲磺酸三甲基硅酯 、 4 A molecular sieve 、 水 作用下， 以 乙醚 、 丙酮 为溶剂， 反应 2.5h， 生成 O-(2,3,4,6-tetra-O-benzyl-α-D-mannopyranosyl)-(1->4)-2-azido-3,6-di-O-benzyl-2-deoxy-α/β-D-glucopyranose
  参考文献：
  名称：

  Glycosyl Inositol Derivatives Related to Inositolphosphoglycan Mediators: Synthesis, Structure, and Biological Activity

  摘要：

  DOI：

  10.1002/(sici)1521-3765(19990104)5:1<320::aid-chem320>3.0.co;2-k
• 作为产物：
  描述：

  甲基2,3,4,6-四-O-苄基-D-吡喃甘露糖苷 在 硫酸 、 potassium carbonate 、 溶剂黄146 作用下， 以 水 为溶剂， 反应 14.5h， 生成 2,3,4,6-tetra-O-benzyl-β-D-mannopyranose 1-O-trichloroacetimidate
  参考文献：
  名称：

  Cardiac glycosides. 7. Sugar stereochemistry and cardiac glycoside activity

  摘要：

  Digitoxigenin alpha-L-, beta-L-, alpha-D-, and beta-D-glucosides; alpha-L-, beta-L-, alpha-D-, and beta-D-mannosides; and alpha-L- and beta-L-rhamnosides were stereoselectively synthesized from the corresponding sugar tetrabenzyl trichloroacetimidates. The Na+,K+-ATPase receptor inhibitory activities of these glycosides (as a measure of receptor binding) were compared with those of digitoxigenin, digitoxigenin 6'-hydroxy-beta-D-digitoxoside, digitoxigenin beta-D-galactoside, and digitoxigenin beta-D-digitoxoside. The observed activities reveal that a given sugar substituent may have a role in binding of some glycoside stereoisomers, but not others. With alpha-L- and possibly beta-L-rhamnosides, the 5'-CH3 and 4'-OH appear to have a predominant role in binding to the Na+,K+-ATPase receptor. Addition of a 6'-OH to form the corresponding mannosides dramatically disrupts the effect of both the 5'-CH3 and 4'-OH in prompting receptor binding of the alpha-L isomer. However, with the beta-L isomer, some influence of 4'-OH, 3'-OH, and 2'-OH binding remains. With beta-D-glycosides, binding via the "5'-CH3 site" appears to be of little importance and addition of a 6'-OH diminishes activity only slightly. With these beta-D-glycosides, an equatorial 4'-OH, axial 3'-OH, and equatorial 2'-OH groups appear to contribute to binding.

  DOI：

  10.1021/jm00160a025

文献信息

• Tris(pentafluorophenyl)borane-Promoted Stereoselective Glycosylation with Glycosyl Trichloroacetimidates under Mild Conditions
  作者：Kunj Bihari Mishra、Adesh Kumar Singh、Jeyakumar Kandasamy

  DOI：10.1021/acs.joc.8b00215

  日期：2018.4.6

  Tris(pentafluorophenyl)borane-promoted stereoselective glycosylation with trichloroacetimidate glycosyl donors is described. The reactions proceed efficiently with a wide range of acceptors, from sugar to nonsugar, under mild conditions in the presence of a catalytic amount of B(C6F5)3. The perbenzylated glucosyl α-imidate provides β-selective glycosides in 70–92% yields.

  描述了用三氯乙酰亚胺酸酯糖基供体的三（五氟苯基）硼烷促进的立体选择性糖基化。在催化量的B（C 6 F 5）3存在下，在温和条件下，反应可利用各种受体（从糖到非糖）有效地进行。过苄基化的葡萄糖基α-亚氨酸酯以70-92％的产率提供β-选择性糖苷。
• First Examples of α-(1→4)-Glycosylation Reactions on Ionic Liquid Supports
  作者：Matthieu Pépin、Marie Hubert-Roux、Claudette Martin、Fréderic Guillen、Catherine Lange、Géraldine Gouhier

  DOI：10.1002/ejoc.201000754

  日期：2010.11

  We have developed the first α-(1→4)-glycosylation reactions on ionic liquid supports. The purification steps involve simple liquid/liquid extractions. The positive influence of the soluble support on the stereoselectivity was proved, and the recyclable character of the ionic liquid was demonstrated.

  我们在离子液体载体上开发了第一个 α-(1→4)-糖基化反应。纯化步骤包括简单的液/液萃取。证明了可溶性载体对立体选择性的积极影响，并证明了离子液体的可回收性。
• Glycosylation with Trichloroacetimidates in Ionic Liquids:  Influence of the Reaction Medium on the Stereochemical Outcome
  作者：Anna Rencurosi、Luigi Lay、Giovanni Russo、Enrico Caneva、Laura Poletti

  DOI：10.1021/jo050704x

  日期：2005.9.1

  [GRAPHICS]The glycosylation with trichloroacetimidates derived from different glycopyranoses bearing a nonparticipating group at C-2 was explored in different ionic liquids as solvents. The stereoselectivity of the reaction was significantly affected by the reaction media and by the anomeric configuration of the donor.
• Glycosyl Inositol Derivatives Related to Inositolphosphoglycan Mediators: Synthesis, Structure, and Biological Activity
  作者：Hansjörg Dietrich、Juan Felix Espinosa、José Luis Chiara、Jesús Jimenez-Barbero、Yolanda Leon、Isabel Varela-Nieto、José-Maria Mato、Felix H. Cano、Concepción Foces-Foces、Manuel Martín-Lomas

  DOI：10.1002/(sici)1521-3765(19990104)5:1<320::aid-chem320>3.0.co;2-k

  日期：1999.1.4
• Cardiac glycosides. 7. Sugar stereochemistry and cardiac glycoside activity
  作者：Hargovind Rathore、Arthur H. L. From、Khalil Ahmed、Dwight S. Fullerton

  DOI：10.1021/jm00160a025

  日期：1986.10

  Digitoxigenin alpha-L-, beta-L-, alpha-D-, and beta-D-glucosides; alpha-L-, beta-L-, alpha-D-, and beta-D-mannosides; and alpha-L- and beta-L-rhamnosides were stereoselectively synthesized from the corresponding sugar tetrabenzyl trichloroacetimidates. The Na+,K+-ATPase receptor inhibitory activities of these glycosides (as a measure of receptor binding) were compared with those of digitoxigenin, digitoxigenin 6'-hydroxy-beta-D-digitoxoside, digitoxigenin beta-D-galactoside, and digitoxigenin beta-D-digitoxoside. The observed activities reveal that a given sugar substituent may have a role in binding of some glycoside stereoisomers, but not others. With alpha-L- and possibly beta-L-rhamnosides, the 5'-CH3 and 4'-OH appear to have a predominant role in binding to the Na+,K+-ATPase receptor. Addition of a 6'-OH to form the corresponding mannosides dramatically disrupts the effect of both the 5'-CH3 and 4'-OH in prompting receptor binding of the alpha-L isomer. However, with the beta-L isomer, some influence of 4'-OH, 3'-OH, and 2'-OH binding remains. With beta-D-glycosides, binding via the "5'-CH3 site" appears to be of little importance and addition of a 6'-OH diminishes activity only slightly. With these beta-D-glycosides, an equatorial 4'-OH, axial 3'-OH, and equatorial 2'-OH groups appear to contribute to binding.