pentachlorophenyl C-(2,3,4,6-tetra-O-acetyl-1-bromo-1-deoxy-β-D-galactopyranosyl)formate | 502186-10-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: pentachlorophenyl C-(2,3,4,6-tetra-O-acetyl-1-bromo-1-deoxy-β-D-galactopyranosyl)formate
• 英文别名: pentachlorophenyl 3,4,5,7-tetra-O-acetyl-2-bromo-2-deoxy-α-D-galacto-hept-2-ulopyranosonate
• CAS: 502186-10-9
• 化学式: C₂₁H₁₈BrCl₅O₁₁
• 分子量: 703.536
• InChiKey: LWOOEWULTOPXBT-GKZWMJKZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.71
• 重原子数：
  38.0
• 可旋转键数：
  7.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  140.73
• 氢给体数：
  0.0
• 氢受体数：
  11.0

反应信息

• 作为反应物：
  描述：

  pentachlorophenyl C-(2,3,4,6-tetra-O-acetyl-1-bromo-1-deoxy-β-D-galactopyranosyl)formate 在 三乙胺 、 silver carbonate 作用下， 以 1,4-二氧六环 为溶剂， 反应 96.0h， 生成 N-[(1R)-2,3,4,6-tetra-O-acetyl-1,5-anhydro-D-galactitolspiro[1.4]-2-methyl-2-oxazolin-5-ylidene]-L-alanine methylester
  参考文献：
  名称：

  Ritter-type reaction of C-(1-bromo-1-deoxy-d-glycopyranosyl)formamides and its application for the synthesis of oligopeptides incorporating anomeric α-amino acids

  摘要：

  O-Peracetylated or -perbenzoylated C-(1-bromo-1-deoxy-D-glycopyranosyl)formamides of D-gluco, D-galacto, and D-arabino configuration were reacted with Ag(I)-salts or HgO in nitrile solvents to give N-acyl-1-cyano-D-glycopyranosylamines with an axial C-N bond at the anomeric centre. In the presence of HgBr2, Hg(CN)(2), or InCl3 the anomer of the above glycosylamine with an equatorial C-N bond was also isolated or detected. In CH3NO2 solutions as few as 5-10 equiv of the nitrile were sufficient to get acceptable yields for the products. Under similar conditions N-substituted C-(2,3,4,6-tetra-O-acetyl-1-bromo-1-deoxy-beta-D-galactopyranosyl)formamides gave anomeric spiro-oxazoline derivatives which, upon mild acidic hydrolysis, opened up to di- and tripeptides of anomeric alpha-amino acids. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2011.07.001
• 作为产物：
  描述：

  3,4,5,7-tetra-O-acetyl-2,6-anhydro-D-glycero-L-manno-heptonic acid 在 溴 、 potassium carbonate 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 、 氯仿 为溶剂， 生成 pentachlorophenyl C-(2,3,4,6-tetra-O-acetyl-1-bromo-1-deoxy-β-D-galactopyranosyl)formate
  参考文献：
  名称：

  端基α-叠氮酸（2-叠氮基-2-脱氧-庚二酸-吡喃二酸）衍生物在掺入糖氨基酸的肽上的应用

  摘要：

  Per- ø -acylated的2,6-脱水aldoheptonic酸D-甘油基-D-庚和D-甘油基-1-甘露配置由相应aldonamides的亚硝化过程得到转化入甲基- ，叔丁基- ，2，按照标准程序，得到2,2-三氯乙基和五氯苯基酯，酰氯和甘氨酰胺。在Bz 2 O 2或AIBN或CH 2中的Na 2 S 2 O 4 –KBrO 3存在下，通过溴在沸腾的CHCl 3中在光照下进行溴化，或在沸腾的CCl 4中在NBS中进行自由基介导的溴化。在室温下使用2 Cl 2-水两相溶剂混合物，得到上述酯和酰氯的2-溴化物的轴向异构体（2-溴-2-脱氧-α-d-庚-2--2-吡喃磺酸衍生物），而甘氨酰胺沿–H 2 C–NH–键分裂。通过将甘氨酸酯与五氯苯基2-溴-2-脱氧-磺基磺酸酯进行N-酰化，获得甘氨酰胺的端基溴化物。在该反应中，轴向异头溴化物证明是稳定的。使用DMSO或DMF中的叠氮化钠替代异

  DOI：

  10.1016/j.tetasy.2004.11.064

文献信息

• Radical-mediated bromination of carbohydrate derivatives: searching for alternative reaction conditions without carbon tetrachloride
  作者：Katalin Czifrák、László Somsák

  DOI：10.1016/s0040-4039(02)02205-0

  日期：2002.12

  KBrO3–Na2S2O4 in CH2Cl2–H2O or PhCF3–H2O biphasic solvent systems was applied to the bromination of several monosaccharide derivatives having capto-datively substituted reaction centres. With less reactive compounds neat PhCF3 was shown to be a suitable substitute of the health and environmentally hazardous carbon tetrachloride.

  在CH 2 Cl 2 -H 2 O或PhCF 3 -H 2 O双相溶剂体系中的KBrO 3 -Na 2 S 2 O 4被用于溴化具有巯基取代反应中心的几种单糖衍生物。活性较低的化合物表明，纯净的CFCF 3是健康和对环境有害的四氯化碳的合适替代品。