3,4,6-tri-O-acetyl-2-deoxy-2-trifluoroacetamido-α-D-glucospyranosyl bromide | 6736-63-6

• 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-2-trifluoroacetamido-α-D-glucospyranosyl bromide
• 英文别名: 3,4,6-tri-O-acetyl-2-deoxy-2-trifluoroacetamido-α-D-glucopyranosyl bromide；2-Deoxy-2-[(trifluoroacetyl)amino]-3,4,6-triacetate-alpha-D-glucopyranosyl Bromide；[(2R,3S,4R,5R,6R)-3,4-diacetyloxy-6-bromo-5-[(2,2,2-trifluoroacetyl)amino]oxan-2-yl]methyl acetate
• CAS: 6736-63-6
• 化学式: C₁₄H₁₇BrF₃NO₈
• 分子量: 464.19
• InChiKey: BSWHDJQWFUUELQ-OOCWMUITSA-N

物化性质

• 熔点：
  92-94 °C
• 沸点：
  483.0±45.0 °C(Predicted)
• 密度：
  1.58±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  27
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  117
• 氢给体数：
  1
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  3,4,6-tri-O-acetyl-2-deoxy-2-trifluoroacetamido-α-D-glucospyranosyl bromide 在 palladium on activated charcoal 2,6-二甲基吡啶 、 Dowex-H⁽¹⁺⁾ 、 氢气 、 potassium carbonate 、 胍 作用下， 以 1,2-二氯乙烷 、 乙腈 为溶剂， 反应 1.5h， 生成 Phosphoric acid mono-[(2S,3R,4R,5S,6R)-4,5-dihydroxy-6-hydroxymethyl-3-(2,2,2-trifluoro-acetylamino)-tetrahydro-pyran-2-yl] ester; compound with triethyl-amine
  参考文献：
  名称：

  方便合成α-和β-d-葡糖胺-1-磷酸及其衍生物

  摘要：

  α-和β-d-氨基葡萄糖-1-磷酸酯的衍生物以及α-d-半乳糖胺-1-磷酸酯以及游离的β-d-氨基葡萄糖-1-磷酸酯的衍生物通过立体选择性地制备。衍生自相应的3,4,6-三-O-乙酰基-2-脱氧-2-三氟乙酰胺基-α-d-己基吡喃糖基溴化物与磷酸二苄酯的1，2-恶唑啉的开口。

  DOI：

  10.1016/s0040-4039(98)01838-3
• 作为产物：
  描述：

  1,3,4,6-tetra-O-acetyl-2-deoxy-2-(4-methoxybenzylidene)amino-β-D-glucopyranose 在 盐酸 、 溴化钛(IV) 、 1-乙酰基-2-苯基肼 作用下， 以 二氯甲烷 、 乙酸乙酯 、 丙酮 为溶剂， 反应 7.0h， 生成 3,4,6-tri-O-acetyl-2-deoxy-2-trifluoroacetamido-α-D-glucospyranosyl bromide
  参考文献：
  名称：

  Synthesis and induction of apoptosis in B cell chronic leukemia by diosgenyl 2-amino-2-deoxy-β-d-glucopyranoside hydrochloride and its derivatives

  摘要：

  2-Acetamido-2-deoxy-D-glucose hydrochloride (D-glucosamine hydrochloride) has been used for the preparation of 1,3.4.6-tetra- O-acetyl-2-deoxy-2-trifluoroacetqamido-beta- (4) and 2-tetrachlorophthalimido-alpha, beta-D-glucopyranose (6) which have been transformed into the appropriate bromides and the chloride. Both bromo and chloro sugars were used as a glycosyl donors for the glycosylation of diosgenin [(25R)-spirost-5-en-3beta-ol]. These condensations were conducted under mild conditions, using silver triflate as a promoter, and gave diosgenyl glycosides 9 and 12. Each of them was converted into diosgenyl 2-amino-2-deoxy-beta-D-glucopyranoside hydrochloride (11) and N-acylamido derivatives. The structures of all new glycosides were established by H-1 and C-13 NMR spectroscopy. These diosgenyl glycosides are the first saponins containing the D-glucosamine residue that have been synthesized. These compounds show promising antitumor activities, The synthetic saponins increase the number of apoptotic B cells, in combination with cladribine (2-CdA). that are isolated from chronic lymphotic leukemia (B-CLL) patients. (C) 2002 Published by Elsevier Science Lid.

  DOI：

  10.1016/s0008-6215(02)00407-x

文献信息

• Novel Chimeric Scaffolds to Extend the Exploration of Receptor Space:  Hybrid β-<scp>d</scp>-Glucose−Benzoheterodiazepine Structures for Broad Screening. Effect of Amide Alkylation on the Course of Cyclization Reactions
  作者：Leïla Abrous、Patrick A. Jokiel、Sarah R. Friedrich、John Hynes,、Amos B. Smith、Ralph Hirschmann

  DOI：10.1021/jo0352068

  日期：2004.1.1

  functionalized analogues (−)-96 and (−)-97 afforded the corresponding dimers (−)-98 and (−)-99, respectively, under a variety of reaction conditions, even at concentrations of only 0.001 N. Consideration of factors affecting the conformation of amide bonds and their effects on cyclization reactions led us to alkylate the amide bond. As expected, the cyclization of the N-methyl derivative (−)-110 afforded exclusively

  设计，合成并功能化了新的分子平台，该平台是两个支架（β- d-葡萄糖和苯并二氮杂hybrid）的杂交体，每个支架都可以结合几种蛋白质，可以用作广泛生物学筛选的探针。在这里，我们描述了这些新型嵌合支架的合成和化学性质。尝试将官能化的类似物（-）- 96和（-）- 97环化，得到相应的二聚体（-）- 98和（-）- 99在各种反应条件下，甚至在浓度仅为0.001 N的情况下也是如此。考虑到影响酰胺键构象的因素及其对环化反应的影响，我们使酰胺键烷基化。如所预期的，N-甲基衍生物（-）- 110的环化仅提供了单分子环化产物（+）- 111。这些化合物现在才进行广泛的筛选，因此目前代表着“勘探库”。
• Probing Synergy between Two Catalytic Strategies in the Glycoside Hydrolase <i>O</i>-GlcNAcase Using Multiple Linear Free Energy Relationships
  作者：Ian R. Greig、Matthew S. Macauley、Ian H. Williams、David J. Vocadlo

  DOI：10.1021/ja904506u

  日期：2009.9.23

  revealing changes in mechanism, transition state, and rate-determining step upon concomitant variation of both nucleophilic strength and leaving group abilities are observed. The observed changes in mechanism reflect the roles played by the enzymic general acid and the catalytic nucleophile. Significantly, these results illustrate how the enzyme synergistically harnesses both modes of catalysis; a feature that

  人类 O-GlcNAcase 在调节丝氨酸和苏氨酸残基与 β-O 连接的 N-乙酰氨基葡萄糖单糖单元 (O-GlcNAc) 的翻译后修饰方面发挥着重要作用。O-GlcNAcase 的机制涉及底物的 2-乙酰氨基基团的亲核参与以取代糖苷连接的离去基团。这种酶对底物结构变化的耐受性使我们能够使用几个系列的底物来表征 O-GlcNAcase 过渡态，以产生多个同时的自由能关系。观察到伴随亲核强度和离去基团能力变化的机制、过渡态和速率决定步骤的变化模式。观察到的机制变化反映了酶通酸和催化亲核试剂所起的作用。重要的是，这些结果说明了酶如何协同利用两种催化模式；许多小分子催化模型都没有的特征。这些研究还表明了氧代碳鎓离子中间体在 O-GlcNAcase 催化的氨基葡萄糖水解中的动力学意义，探索了使用酶过渡态结构的非原子研究可能学到的知识的局限性，并提供了关于保留超家族的一般见解糖苷水解酶作为有效的催化剂。
• UDP-N-trifluoroacetylglucosamine as an alternative substrate in N-acetylglucosaminyltransferase reactions
  作者：Rafael F. Sala、Shawna L. MacKinnon、Monica M. Palcic、Martin E. Tanner

  DOI：10.1016/s0008-6215(97)10033-7

  日期：1998.1

  The synthesis of UDP-N-trifluoroacetylglucosamine [uridine 5'-(2-trifluoroacetamido-2-deoxy-alpha-D-glucopyranosyl diphosphate, UDP-GlcNAc-F3] is reported. The compound is found to serve as a substrate for the core-2 GlcNAc transferase (EC 2.4.1.102) that is involved in the biosynthesis of O-linked glycoproteins and for the GlcNAcT-V transferase (EC 2.4.1.155) that is a key biosynthetic enzyme controlling

  6）-使用GlcNAcT-V转移酶的β-D-Glcp-OR[R ＝（CH 2）7 CH 3]。在温和的碱性条件下除去三氟乙酰基，得到相应的含葡糖胺的四糖。这些实施例证明了使用GlcNAc特异性转移酶将掩蔽形式的葡糖胺残基引入寡糖的可行性。对于三氟乙酰氨基基团作为特定识别元件的要求在以下观察中显而易见：UDP-葡萄糖胺和UDP-葡萄糖均不能充当core-2 GlcNAc转移酶的供体底物。这些实施例证实了使用GlcNAc特异性转移酶将掩蔽形式的葡糖胺残基引入寡糖的可行性。对于三氟乙酰氨基基团作为特定识别元件的要求在以下观察中显而易见：UDP-葡萄糖胺和UDP-葡萄糖均不能充当core-2 GlcNAc转移酶的供体底物。这些实施例证明了使用GlcNAc特异性转移酶将掩蔽形式的葡糖胺残基引入寡糖的可行性。对于三氟乙酰氨基基团作为特定识别元件的要求在以下观察中显而易见：UDP-葡萄糖胺和UDP-葡萄糖均不能充当core-2
• OLIGONUCLEOTIDE DERIVATIVE, OLIGONUCLEOTIDE CONSTRUCT USING THE SAME, AND METHODS FOR PRODUCING THEM
  申请人：GIFU UNIVERSITY

  公开号：US20180094017A1

  公开（公告）日：2018-04-05

  The oligonucleotide derivative of the present invention is represented by Formula (1). This derivative is considered to be introduced into cells by binding of its amino sugar chain moiety to a ligand on cell surfaces, and have selective drug delivery function. The oligonucleotide derivative can be easily synthesized and introduced into cells without using a lipofection reagent. wherein—A and B are independently modified or unmodified oligonucleotides whose total chain length is 3 or more, and A and B do not contain hydroxyl groups at 3′ and 5′ ends of the oligonucleotide; S represents a sugar substituent, a peptide chain, or a tocopherol-binding group; and an alkyl group may be bound instead of hydrogen bound to a benzene ring.

  本发明的寡核苷酸衍生物由式（1）表示。该衍生物被认为通过其氨基糖链部分与细胞表面的配体结合而被引入细胞，并具有选择性药物传递功能。该寡核苷酸衍生物可以在不使用脂质体载体的情况下轻松合成并引入细胞。其中，A和B分别是经修饰或未经修饰的寡核苷酸，其总链长为3或更长，且A和B不含有寡核苷酸的3′和5′末端的羟基；S代表糖取代基、肽链或生育酚结合基；和烷基基团可以与苯环上的氢结合而不是氢结合。
• Long chain alkyl and fluoroalkyl glucose and glucosamine derivatives as hyaluronic acid subunits—Scaffolds for drug delivery
  作者：Katarzyna Koroniak-Szejn、Joanna Tomaszewska、Jakub Grajewski、Henryk Koroniak

  DOI：10.1016/j.jfluchem.2019.01.004

  日期：2019.3

  Synthesis of hyaluronic acid components modified with long alkyl or fluorinated alkyl chain has been described as potential scaffold for drug delivery systems. The strategy of introducing fluorinated motifs in sugar anomeric position via “click” reaction has been studied showing various reactivity when position 2 was substituted with trichloro- and trifluoroamide unit. To determine the conformations

  已经描述了用长烷基或氟化烷基链修饰的透明质酸组分的合成作为药物递送系统的潜在支架。已经研究了通过“点击”反应在糖异头位置引入氟化基序的策略，该策略在位置2被三氯和三氟酰胺单元取代时显示出各种反应性。为了确定酰化葡萄糖或葡糖胺的模型1,2,3-三唑取代衍生物的构象，记录了CD光谱，并通过分子建模来支持构象分析。