1,2:5,6-di-O-isoprolylidene-3-C-trichloromethyl-α-D-allofuranose | 689218-37-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,2:5,6-di-O-isoprolylidene-3-C-trichloromethyl-α-D-allofuranose
• 英文别名: 1,2:5,6-di-O-isopropylidene-3-C-trichloromethyl-α-D-allofuranose；1,2:5,6-di-O-isopropylidene-3-C-trichloromethyl-α-D-allose；(3aR,5R,6R,6aR)-5-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-6-(trichloromethyl)-5,6a-dihydro-3aH-furo[2,3-d][1,3]dioxol-6-ol
• CAS: 689218-37-9
• 化学式: C₁₃H₁₉Cl₃O₆
• 分子量: 377.649
• InChiKey: BWAWRWHDKBFYQY-LOLAFCHLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  22
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  66.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1,2:5,6-di-O-isoprolylidene-3-C-trichloromethyl-α-D-allofuranose 在 sodium tetrahydroborate 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 甲醇 为溶剂， 反应 4.25h， 生成 3-chloro-3-deoxy-3-C-hydroxymethyl-1,2:5,6-di-O-isopropylidene-α-D-glucofuranose
  参考文献：
  名称：

  Halogenated d-xylono-δ-lactams: synthesis and enzyme inhibition study

  摘要：

  A concise synthesis of four C-3 fluoro/chloro-D-xylono-delta-lactams 3/4 has been reported. The methodology involves Corey-Link approach with suitably protected 3-oxo-D-gluco-furanose to introduce F/Cl as well as ester/amide functionalities at C-3 of glucose. In next steps, 5,6-O-isopropylidene group was converted to the 5-azido xylosugars that on opening of 1,2-acetonide group, and intramolecular Schmidt-Boyer reaction with TFA/H2O, in one pot, afforded lactams 3/4. Conformational aspect of delta-lactams was studied by the H-1 NMR spectroscopy. The halogenated d-lactams 3/4 showed no inhibition against different glycosidase enzymes. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2014.10.023
• 作为产物：
  描述：

  1,2:5,6-二异亚丙基-alpha-D-异呋喃糖 在 pyridinium chlorochromate 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 反应 3.3h， 生成 1,2:5,6-di-O-isoprolylidene-3-C-trichloromethyl-α-D-allofuranose
  参考文献：
  名称：

  糖类呋喃类反式邻位二酸作为γ转角诱导剂：合成和构象研究†

  摘要：

  一种简单的合成糖呋喃类反式二邻苯二甲酸二酸并将其掺入N端四肽序列的简单方法（H-苯丙氨酸-色氨酸-赖氨酸-Thr-OH）已经获得了糖肽8。2D NMR和MD的模拟研究8清楚地表明，糖二酸采用朝向所述N-末端的γ-转构象。

  DOI：

  10.1039/c3ob41462k

文献信息

• An Alternative Synthesis of Some Carbohydrate α-Amino Acids
  作者：Grant S. Forman、Adrian Scaffidi、Robert V. Stick

  DOI：10.1071/ch03214

  日期：——

  alcohols. A subsequent treatment of these alcohols under Corey–Link conditions (base, sodium azide, methanol) has given rise to α-azido esters, transformable into azido acids, amino esters, and amino acids. An amino ester and an azido acid have been coupled to form a dipeptide.

  几种碳水化合物酮已转化为它们的三氯甲基支链叔醇。随后在 Corey-Link 条件（碱、叠氮化钠、甲醇）下对这些醇进行处理产生了 α-叠氮酯，可转化为叠氮酸、氨基酯和氨基酸。氨基酯和叠氮酸已偶联形成二肽。
• The Synthesis of Carbohydrate α-Amino Acids Utilizing the Corey - Link Reaction
  作者：Adrian Scaffidi、Brian W. Skelton、Robert V. Stick、Allan H. White

  DOI：10.1071/ch04015

  日期：——

  Various carbohydrate ketones (uloses) have been treated with chloroform under strongly basic conditions to yield trichloromethyl tertiary alcohols. These alcohols, when subjected to the conditions of the modified Corey–Link reaction (sodium azide and 1,8-diazabicyclo[5.4.0]undec-7-ene in methanol), generally gave the expected azido ester with complete stereocontrol. Subsequent transformations on these

  已在强碱性条件下用氯仿处理各种碳水化合物酮（乌洛糖）以产生三氯甲基叔醇。这些醇在经受改进的 Corey-Link 反应条件（叠氮化钠和甲醇中的 1,8-二氮杂双环[5.4.0] undec-7-ene）条件下，通常会产生具有完全立体控制的预期叠氮基酯。这些叠氮基酯的后续转化提供了氨基酯、叠氮基酸，在一种情况下还提供了氨基酸。应用于受保护的 d-glucono-1,5-lactone 的类似序列仅部分成功。据报道 1,2:5,6-di-O-isopropylidene-3-C-trichloromethyl 的单晶 X 射线结构-α-d-阿洛糖，(3S)-3-C-azido-3-C-carboxy-3-deoxy-1,2:5,6-di-O-isopropylidene-α-d-ribo-hexose, 1 ,2:5,6-di-O-cyclohexylidene-3-C-trichloromethyl-α-d-gulose
• Stereocontrolled synthesis of (5+5), (5+6) and (6+6) 3-spiropseudonucleosides
  作者：Consolación Gasch、José M. Illangua、Penélope Merino-Montiel、José Fuentes

  DOI：10.1016/j.tet.2009.03.038

  日期：2009.5

  3-Spiropseudonucleosides, in which the heterocyclic base is a five-membered (oxazolidine, imidazolidine, thiohydantoin) or six-membered (perhydrooxazine) heterocycle, have been prepared starting from a hexofuranos-3-ulose. The method leads to good yields and is completely stereoselective. The key intermediate is a sugar iso(thio)cyanate.

  已经从六呋喃糖-3-基糖开始制备了3-螺伪假核苷，其中杂环碱基是五元（恶唑烷，咪唑烷，硫代乙内酰脲）或六元（全氢恶嗪）杂环。该方法产生了良好的产率，并且是完全立体选择性的。关键中间体是糖异（硫）氰酸酯。
• An Expansion of the Role of the Corey - Link Reaction for the Synthesis of α-Substituted Carboxylic Acid Esters
  作者：Adrian Scaffidi、Brian W. Skelton、Robert V. Stick、Allan H. White

  DOI：10.1071/ch06137

  日期：——

  Under the conditions of the modified Corey–Link reaction but with a nucleophile different from the usual azide, a range of α-substituted carboxylic acid esters (and one amide) has been obtained. A similar addition of bromoform to the ulose has formed the α-bromo methyl ester. Two attempts at forming an ‘inositol α-amino acid’ from a polyhydroxylated cyclohexanone failed.Single-crystal X-ray structure

  在碱性条件下用氯仿处理 1,2:5,6-二-O-异亚丙基-α-d-核糖-己糖-3-乌洛糖，得到正常的 3-C-三氯甲基-α-d-别呋喃糖衍生物。在改进的 Corey-Link 反应条件下，但使用不同于通常叠氮化物的亲核试剂，获得了一系列 α-取代的羧酸酯（和一种酰胺）。将溴仿类似地添加到乌洛糖中形成了α-溴甲酯。从多羟基化环己酮形成“肌醇 α-氨基酸”的两次尝试都失败了。单晶 X 射线结构测定报告用于 (3S)-1,2:5,6-di-O-isopropylidene-3-C -甲氧基羰基-3-S-苯基-3-硫代-α-d-核糖-己糖，(3S)-1,2:5,6-二-O-异亚丙基-3-S-苯基-3-C-(苯硫基）羰基-3-硫代-α-d-核糖-己糖，3-deoxy-1,2:5，