3,4,6-tri-O-acetyl-2-deoxy-α-D-glucopyranosyl chloride | 88580-20-5

• 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: 3,4,6-tri-O-acetyl-2-deoxy-α-D-glucopyranosyl chloride
• 英文别名: [(2R,3S,4R,6R)-3,4-diacetyloxy-6-chlorooxan-2-yl]methyl acetate
• CAS: 88580-20-5
• 化学式: C₁₂H₁₇ClO₇
• 分子量: 308.716
• InChiKey: GEGZZOKVBPFVIF-WYUUTHIRSA-N

物化性质

• 沸点：
  380.0±42.0 °C(Predicted)
• 密度：
  1.29±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  20
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  88.1
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  3,4,6-tri-O-acetyl-2-deoxy-α-D-glucopyranosyl chloride 在 咪唑 、 正丁基锂 、 重水 、 sodium methylate 、 碳酸氢钠 、 lithium dihydronaphthylide radical 、 N,N-二异丙基乙胺 、 间氯过氧苯甲酸 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 53.17h， 生成 1-[(2S,4R,5R,6R)-4,5-Bis-(tert-butyl-dimethyl-silanyloxy)-6-(tert-butyl-dimethyl-silanyloxymethyl)-tetrahydro-pyran-2-yl]-2-methyl-propan-1-ol
  参考文献：
  名称：

  2-脱氧-D-吡喃葡萄糖基苯基砜的制备和还原锂化：对C-糖苷的高度立体选择性

  摘要：

  2-脱氧-D-吡喃葡萄糖基苯基砜3a-c已从商品三-O-乙酰基-D-葡萄糖1合成，产率为75-83％。它们通过萘二甲酸锂的还原性脱磺酰基作用以及中间体糖基锂5与醛的反应导致具有高立体选择性的α-DC-吡喃葡萄糖苷。

  DOI：

  10.1016/s0040-4039(00)95048-2
• 作为产物：
  描述：

  乙酰化葡萄烯糖 在 盐酸 作用下， 以 甲苯 为溶剂， 反应 1.0h， 生成 3,4,6-tri-O-acetyl-2-deoxy-α-D-glucopyranosyl chloride
  参考文献：
  名称：

  2-脱氧-D-吡喃葡萄糖基苯基砜的制备和还原锂化：对C-糖苷的高度立体选择性

  摘要：

  2-脱氧-D-吡喃葡萄糖基苯基砜3a-c已从商品三-O-乙酰基-D-葡萄糖1合成，产率为75-83％。它们通过萘二甲酸锂的还原性脱磺酰基作用以及中间体糖基锂5与醛的反应导致具有高立体选择性的α-DC-吡喃葡萄糖苷。

  DOI：

  10.1016/s0040-4039(00)95048-2

文献信息

• Stereoselective Preparation of <i>C</i> ‐Aryl Glycosides <i>via</i> Visible‐Light‐Induced Nickel‐Catalyzed Reductive Cross‐Coupling of Glycosyl Chlorides and Aryl Bromides
  作者：Ze‐Dong Mou、Jia‐Xi Wang、Xia Zhang、Dawen Niu

  DOI：10.1002/adsc.202100343

  日期：2021.6.21

  A nickel-catalyzed cross-coupling reaction of glycosyl chlorides with aryl bromides has been developed. The reaction proceeds smoothly under visible-light irradiation and features the use of bench-stable glycosyl chlorides, allowing the highly stereoselective synthesis of C-aryl glycosides.

  已经开发了一种镍催化的糖基氯与芳基溴的交叉偶联反应。该反应在可见光照射下顺利进行，并使用了实验室稳定的糖基氯，可以高度立体选择性地合成C-芳基糖苷。
• Synthesis of glycosyl chlorides using catalytic Appel conditions
  作者：Imlirenla Pongener、Kirill Nikitin、Eoghan M. McGarrigle

  DOI：10.1039/c9ob01544b

  日期：——

  stereoselective synthesis of glycosyl chlorides using catalytic Appel conditions is described. Good yields of α-glycosyl chlorides were obtained using a range of glycosyl hemiacetals, oxalyl chloride and 5 mol% Ph3PO. For 2-deoxysugars treatment of the corresponding hemiacetals with oxalyl chloride without phosphine oxide catalyst also gave good yields of glycosyl chloride. The method is operationaly

  描述了使用催化Appel条件立体选择性合成糖基氯。使用一定范围的糖基半缩醛，草酰氯和5 mol％的Ph3PO，可获得高产率的α-糖基氯。对于2-脱氧糖，在没有氧化膦催化剂的情况下用草酰氯处理相应的半缩醛也得到了良好的糖基氯收率。该方法操作简单，并且可以容易地除去5mol％的氧化膦副产物。或者，可以进行一锅多催化剂糖基化以将糖基半缩醛直接转化为糖苷。
• Stereoselective <i>O</i> ‐Glycosylations by Pyrylium Salt Organocatalysis**
  作者：Michael Martin Nielsen、Thomas Holmstrøm、Christian Marcus Pedersen

  DOI：10.1002/anie.202115394

  日期：2022.2

  A glycosylation method for non-specialists: Commercially available pyrylium salts catalyze stereoselective glycosylation reactions with trichloroacetimidate electrophiles. A wide range of phenolic nucleophiles are compatible with the procedure. The standard conditions involve mixing three components at ambient conditions and proceed with minimal formation of undesired by-products.

  非专业人士的糖基化方法：市售的吡喃盐催化立体选择性糖基化反应与三氯乙酰亚胺酯亲电子试剂。多种酚类亲核试剂与该程序兼容。标准条件包括在环境条件下混合三种组分，并以最少的不希望的副产物形成进行。
• Organoboron-Catalyzed Regio- and Stereoselective Formation of β-2-Deoxyglycosidic Linkages
  作者：Thomas M. Beale、Patrick J. Moon、Mark S. Taylor

  DOI：10.1021/ol501711v

  日期：2014.7.3

  A borinic acid derived catalyst enables regioselective and β-selective reactions of 2-deoxy- and 2,6-dideoxyglycosyl chloride donors with pyranoside-derived acceptors having unprotected cis-1,2- and 1,3-diol groups. The use of catalysis to promote a β-selective pathway by enhancement of acceptor nucleophilicity constitutes a distinct approach from previous work, which has been aimed at modulating donor reactivity by variation of protective and/or leaving groups.
• Synthetic approaches to 2-deoxyglycosyl phosphates
  作者：Jutta Niggemann、Thiseb K. Lindhorst、Martina Walfort、Lothar Laupichler、Henry Sajus、Joachim Thiem

  DOI：10.1016/0008-6215(93)84031-z

  日期：1993.8

  By the use of the N-iodosuccinimide (NIS)-procedure, various glycals could be converted into 2-deoxy-2-iodoglycosyl phosphates. Treatment of glycals 1 and 7 with NIS and dibenzyl phosphate gave the corresponding alpha-1,2-trans-diaxial 2-deoxy-2-iodoglycosyl phosphates 2 and 8 as the main products. The beta-1,2-trans-diequatorial compounds 3 and 9 were isolated as by-products. Analogous reaction of glycals 4 and 10 gave the corresponding 2-deoxy-2-iodoglycosyl phosphates 5, 6, 11, and 12 as crude products, which were characterized by H-1 NMR spectroscopy. Classical phosphorylation of 2-deoxyglycosyl chlorides 14 and 16 with silver dibenzyl phosphate gave the corresponding dibenzyl 2-deoxy-alpha-glycosyl phosphates 15 and 17. Alternatively, glycosylation of tri-O-acetyl-D-glucal (1) using dibenzyl phosphate and triphenylphosphine hydrobromide afforded 15 in lower yield. The application of S-(2-deoxyglycosyl) phosphorodithioates as glycosyl donors provided the most convenient way to dibenzyl 2-deoxyglycosyl phosphates. The alpha-glycosyl phosphates 15, 20, and 22 could be synthesized by reaction of the 2-deoxyglycosyl dithiophosphates 18, 19, and 21 with dibenzyl phosphate and activation by iodonium di-sym-collidine perchlorate. Similary, the 2,6-dideoxyglycosyl dithiophosphates 23 and 25 gave the 2,6-dideoxy phosphates 24 and 26; however, the isolation of these labile compounds could not be effected.