methyl 2,4,6-tri-O-benzoyl-α-D-galactopyranoside | 155835-07-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2,4,6-tri-O-benzoyl-α-D-galactopyranoside
• 英文别名: [(2R,3R,4S,5R,6S)-3,5-dibenzoyloxy-4-hydroxy-6-methoxyoxan-2-yl]methyl benzoate
• CAS: 155835-07-7
• 化学式: C₂₈H₂₆O₉
• 分子量: 506.509
• InChiKey: FAZUIGXOWOIOEH-SUWSLWCISA-N

物化性质

• 沸点：
  678.7±55.0 °C(Predicted)
• 密度：
  1.35±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  37
• 可旋转键数：
  11
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  118
• 氢给体数：
  1
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  methyl 2,4,6-tri-O-benzoyl-α-D-galactopyranoside 在 吡啶 、 甲醇 、 sodium azide 、 18-冠醚-6 、 4 A molecular sieve 、 硫酸 、 氢溴酸 、 silver trifluoromethanesulfonate 、 臭氧 、 溶剂黄146 、 三乙胺 、 乙酰氯 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 159.0h， 生成 2-azidoethyl O-(2,4,6-tri-O-benzoyl-β-D-galactopyranosyl)-(1->4)-2-acetamido-6-O-benzoyl-3-O-benzyl-2-deoxy-β-D-glucopyranoside
  参考文献：
  名称：

  Study of glycosylation with N-trichloroacetyl-d-glucosamine derivatives in the syntheses of the spacer-armed pentasaccharides sialyl lacto-N-neotetraose and sialyl lacto-N-tetraose, their fragments, and analogues

  摘要：

  The syntheses of 2-aminoethyl glycosides of the pentasaccharides Neu5Ac-alpha (2 --> 3)-Gal-beta (3(1 --> 4)-GlcNAc-beta (3(1 --> 3)-Gal-beta (1 --> 4)-Glc and Neu5Ac-alpha (2 --> 3)-Gal-beta (1 --> 3)-GlcNAc-beta (1 --> 3)-Gal-beta (1 --> 4)-Glc, their asialo di-, tri-, and tetrasaccharide fragments, and analogues included a systematic study of glycosylation with variously protected mono- and disaccharide donors derived from N-trichloroacetyl-D-glucosamine of galactose, lactose, and lactosamine glycosyl acceptors bearing benzoyl protection around the OH group to be glycosylated. Despite the. low reactivity of these acceptors, stereo specificity and good to excellent yields were obtained with NIS-TfOH-activated thioglycoside donors of such type, or with AgOTf-activated glycosyl bromides, while other promotors, as well as a trichloroacetimidate donor, were less effective, and a beta -acetate donor was inactive. In NIS-TfOH-promoted glycosylation with the thioglycosides, the use of TfOH in catalytic amount led to rapid formation of the corresponding oxazoline, but the quantity of TfOH necessary for further efficient coupling with an acceptor depended on the reactivity of the donor, varying from 0.07 equiv for a 3,6-di-O-benzylated monosaccharide derivative to 2.1 equiv for a peracetylated disaccharide one. In the glycosylation products, the N-trichloroacetyl group was easily converted into N-acetyl by alkaline hydrolysis followed by N-acetylation. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(01)00213-0
• 作为产物：
  描述：

  甲基-D-半乳糖苷-2,3,6-三苯甲酸酯 在 silver(l) oxide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 48.0h， 以44%的产率得到methyl 2,4,6-tri-O-benzoyl-α-D-galactopyranoside
  参考文献：
  名称：

  甲基O-α-L-鼠李糖基-（1→2）-α-D-吡喃半乳糖苷的合成在半乳糖残基的3、4或6位上特别脱氧。

  摘要：

  通过将2,3,4-三-O-苯甲酰基-α-L-鼠李糖基吡喃糖基溴化物与适当保护的甲基α-D-吡喃半乳糖苷的脱氧衍生物缩合来合成标题二糖。通过用N，N'-硫代羰基二咪唑活化被保护的甲基α-D-葡萄糖或半乳糖吡喃糖苷，然后用氢化三丁基锡和偶氮二异丁腈处理，可以实现脱氧。在位置3，当用三-O-苯甲酰化的前体而不是三-O-苄基化的前体进行脱氧更成功。通过甲基3-脱氧-α-D-木糖己吡喃糖苷的苄基化获得相应的亲核试剂。可以从具有D-半乳糖或D-葡萄糖构型的衍生物开始进行在位置4上脱氧的糖基受体的制备。

  DOI：

  10.1016/0008-6215(94)84287-6

文献信息

• Regioselective One-Pot Benzoylation of Triol and Tetraol Arrays in Carbohydrates
  作者：Tong Li、Tianlu Li、Tongxiao Cui、Yajing Sun、Fengshan Wang、Hongzhi Cao、Richard R. Schmidt、Peng Peng

  DOI：10.1021/acs.orglett.8b01446

  日期：2018.7.6

  Protection of 2,3,4-O-unprotected α-galacto- and α-fucopyranosides with BzCN and DMAP/DIPEA as the base afforded directly and regioselectively the 3-O-unprotected derivatives. The rationale for these studies was to take advantage of the eventual cooperativity of the “cyanide effect” and “the alkoxy group mediated diol effect”. This way, even the totally unprotected α-galactopyranosides could be regioselectively

  用BzCN和DMAP / DIPEA作为碱保护2,3,4- O-未保护的α-半乳糖和α-呋喃果糖苷直接和区域选择性地提供了3- O-未保护的衍生物。这些研究的基本原理是利用“氰化物效应”和“烷氧基基团介导的二醇效应”的最终协同作用。这样，甚至完全未保护的α-吡喃半乳糖苷也可以区域选择性地转化为相应的2,4,6- O-保护的衍生物。这些构件的巨大效用已在有效的三糖合成中得到了证明。
• Mapping the Relationship between Glycosyl Acceptor Reactivity and Glycosylation Stereoselectivity
  作者：Stefan van der Vorm、Jacob M. A. van Hengst、Marloes Bakker、Herman S. Overkleeft、Gijsbert A. van der Marel、Jeroen D. C. Codée

  DOI：10.1002/anie.201802899

  日期：2018.7.2

  The reactivity of both coupling partners—the glycosyl donor and acceptor—is decisive for the outcome of a glycosylation reaction, in terms of both yield and stereoselectivity. Where the reactivity of glycosyl donors is well understood and can be controlled through manipulation of the functional/protecting‐group pattern, the reactivity of glycosyl acceptor alcohols is poorly understood. We here present

  就产量和立体选择性而言，两个偶联伙伴（糖基供体和受体）的反应性对糖基化反应的结果都具有决定性作用。如果对糖基供体的反应性了解得很好，并且可以通过功能/保护基团模式的控制来控制，则对糖基受体醇的反应性了解得很少。我们在这里提出了一个操作简单的系统来评估糖基受体的反应性，该系统采用了两个构象锁定的供体，其立体选择性严格取决于亲核试剂的反应性。筛选了大量受体，并建立了它们的结构-反应性/立体选择性关系。通过系统地改变保护基，可以调节糖基受体的反应性以获得立体选择性。顺式葡萄糖基化。
• Synthesis of specifically monofluorinated ligands related to the O-polysaccharide of Shigella dysenteriae type 1
  作者：Laurence A. Mulard、Paul Kováč、Cornelis P.J. Glaudemans

  DOI：10.1016/0008-6215(94)84194-2

  日期：1994.6

  The synthesis is reported of galactopyranose nucleophiles monofluorinated at positions 3, 4, or 6 and protected by 4,6-O-benzylidene, 3,6-di-O-benzyl, or 3,4-O-isopropylidene groups, respectively. The condensation of these nucleophiles with 2,3,4-tri-O-benzoyl-alpha-L-rhamnosyl bromide gave, after deprotection, the disaccharide analogues of methyl O-alpha-L-rhamnopyranosyl-(1-->2)-alpha-D-galactopyranoside

  据报道合成了在3、4或6位单氟化并分别由4，6-O-亚苄基，3，6-二-O-苄基或3，4-O-异亚丙基保护的半乳糖吡喃糖亲核体。这些亲核试剂与2,3,4-三-O-苯甲酰基-α-L-鼠李糖基溴缩合后，脱保护后得到甲基O-α-L-鼠李糖基-（1-> 2）-的二糖类似物。 α-D-半乳糖吡喃糖苷，在半乳糖苷残基的3、4或6位单氟化。
• Regioselective benzoylation of sugars mediated by excessive Bu2SnO: observation of temperature promoted migration
  作者：Zhiyuan Zhang、Chi-Huey Wong

  DOI：10.1016/s0040-4020(02)00661-0

  日期：2002.8

  Regioselective benzoylation of carbohydrates using an excess of dibutyltin oxide (Bu2SnO) at increased reaction temperatures has been developed for the synthesis of several glycoside benzoates with one or two free hydroxyl groups, including galactosides, glucosides, mannosides and lactosides in high yields. These compounds are useful as building blocks for the synthesis of complex saccharides and derivatives. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Study of glycosylation with N-trichloroacetyl-d-glucosamine derivatives in the syntheses of the spacer-armed pentasaccharides sialyl lacto-N-neotetraose and sialyl lacto-N-tetraose, their fragments, and analogues
  作者：Andrei A. Sherman、Olga N. Yudina、Yury V. Mironov、Elena V. Sukhova、Alexander S. Shashkov、Vladimir M. Menshov、Nikolay E. Nifantiev

  DOI：10.1016/s0008-6215(01)00213-0

  日期：2001.11

  The syntheses of 2-aminoethyl glycosides of the pentasaccharides Neu5Ac-alpha (2 --> 3)-Gal-beta (3(1 --> 4)-GlcNAc-beta (3(1 --> 3)-Gal-beta (1 --> 4)-Glc and Neu5Ac-alpha (2 --> 3)-Gal-beta (1 --> 3)-GlcNAc-beta (1 --> 3)-Gal-beta (1 --> 4)-Glc, their asialo di-, tri-, and tetrasaccharide fragments, and analogues included a systematic study of glycosylation with variously protected mono- and disaccharide donors derived from N-trichloroacetyl-D-glucosamine of galactose, lactose, and lactosamine glycosyl acceptors bearing benzoyl protection around the OH group to be glycosylated. Despite the. low reactivity of these acceptors, stereo specificity and good to excellent yields were obtained with NIS-TfOH-activated thioglycoside donors of such type, or with AgOTf-activated glycosyl bromides, while other promotors, as well as a trichloroacetimidate donor, were less effective, and a beta -acetate donor was inactive. In NIS-TfOH-promoted glycosylation with the thioglycosides, the use of TfOH in catalytic amount led to rapid formation of the corresponding oxazoline, but the quantity of TfOH necessary for further efficient coupling with an acceptor depended on the reactivity of the donor, varying from 0.07 equiv for a 3,6-di-O-benzylated monosaccharide derivative to 2.1 equiv for a peracetylated disaccharide one. In the glycosylation products, the N-trichloroacetyl group was easily converted into N-acetyl by alkaline hydrolysis followed by N-acetylation. (C) 2001 Elsevier Science Ltd. All rights reserved.