溴2-脱氧-2-N-邻苯二甲酰亚胺基-3,4,6-三-O-乙酰基-alpha,beta-D-吡喃葡萄糖苷 | 70831-94-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异吲哚及其衍生物
• 中文名称: 溴2-脱氧-2-N-邻苯二甲酰亚胺基-3,4,6-三-O-乙酰基-alpha,beta-D-吡喃葡萄糖苷
• 英文名称: 3,4,6-tri-O-acetyl-2-deoxy-2-phthalimido-D-glucopyranosyl bromide
• 英文别名: 3,4,6-tri-O-acetyl-2-deoxy-2-phthalimido-α-D-glucopyranosyl bromide；[(2R,3S,4R,5R)-3,4-diacetyloxy-6-bromo-5-(1,3-dioxoisoindol-2-yl)oxan-2-yl]methyl acetate
• CAS: 70831-94-6
• 化学式: C₂₀H₂₀BrNO₉
• 分子量: 498.284
• InChiKey: GRDUQQNEXMJRRS-XNIMBYMISA-N

物化性质

• 熔点：
  124-128°C
• 沸点：
  567.1±50.0 °C(Predicted)
• 密度：
  1.59±0.1 g/cm3(Predicted)
• 溶解度：
  可溶于氯仿（少量）、二氯甲烷（少量）、乙酸乙酯（少量）

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  31
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  126
• 氢给体数：
  0
• 氢受体数：
  9

制备方法与用途

用途

用于合成β-D-N-乙酰葡萄糖胺糖苷键。

上下游信息

• 上游原料

  中文名称	英文名称	CAS号	化学式	分子量
  2-脱氧-2-苯二酰亚胺-1,3,4,6-四-氧-乙酰-β-D-吡喃葡萄糖	1,3,4,6-tetra-O-acetyl-2-deoxy-2-phthalimido-β-D-glucopyranose	10022-13-6	C22H23NO11	477.425
  4-甲氧苯基3,4,6-三-O-乙酰-2-脱氧-2-苯二甲酰亚氨基-β-D-吡喃葡萄糖苷	4-methoxylphenzyl 2-deoxy-2-phthalimido-3,4,6-tri-O-acetyl-β-D-glucopyranoside	138906-41-9	C27H27NO11	541.511
  ——	2-deoxy-2-phthalimido-D-glucopyranose	31505-45-0	C14H15NO7	309.276

• 下游产品

  中文名称	英文名称	CAS号	化学式	分子量
  3,4,6-三-O-乙酰基-2-脱氧-2-(1,3-二氧代-1,3-二氢-2H-异吲哚-2-基)-D-吡喃葡萄糖	3,4,6-tri-O-acetyl-2-deoxy-2-phthalimido-D-glucopyranose	72858-55-0	C20H21NO10	435.387
  甲基 3,4,6-O-三乙酰基-2-脱氧-2-邻苯二甲酰亚氨基-beta-D-吡喃葡萄糖苷	methyl 3,4,6-tri-O-acetyl-2-deoxy-2-phthalimido-β-D-glucopyranoside	76101-13-8	C21H23NO10	449.414
  甲基 2-脱氧-2-N-苯二甲酰亚氨基-beta-D-吡喃葡萄糖苷	methyl 2-deoxy-2-phthalimido-β-D-glucopyranoside	76101-14-9	C15H17NO7	323.302
  甲基 3-O-苄基-4,6-O-亚苄基-2-脱氧-2-(1,3-二氧代-1,3-二氢-2H-异吲哚-2-基)吡喃己糖苷	methyl 3-O-benzyl-4,6-O-benzylidene-2-deoxy-2-phthalimido-β-D-glucopyranoside	97276-96-5	C29H27NO7	501.536
  甲基 3,6-二-O-苄基-2-脱氧-2-(1,3-二氧代-1,3-二氢-2H-异吲哚-2-基)吡喃己糖苷	methyl 3,6-di-O-benzyl-2-deoxy-2-phthalimido-β-D-glucopyranoside	97242-79-0	C29H29NO7	503.552
  ——	6-chlorohexyl 3,6-di-O-benzyl-2-deoxy-2-phthalimido-β-D-glucopyranoside	278784-82-0	C34H38ClNO7	608.131
  ——	Methyl 4,6-O-benzylidene-2-deoxy-2-phthalimido-β-D-glucopyranoside	97276-95-4	C22H21NO7	411.411
  ——	methyl 4,6-O-benzylidene-2-N-phthalimido-β-D-mannopyranoside	81927-56-2	C22H21NO7	411.411
  ——	3-benzyloxycarbonylamino-1-propyl 6-O-tert-butyldiphenylsilyl-2-deoxy-2-phthalimido-β-D-glucopyranoside	347391-77-9	C41H46N2O9Si	738.91
  ——	ethyl 6-O-tert-butyldiphenylsilyl-2-deoxy-2-phthalimido-1-thio-β-glucopyranoside	215439-81-9	C32H37NO6SSi	591.8

反应信息

• 作为反应物：
  描述：

  溴2-脱氧-2-N-邻苯二甲酰亚胺基-3,4,6-三-O-乙酰基-alpha,beta-D-吡喃葡萄糖苷 在 盐酸 、 4 Angstroem MS 、 lutidine 、 sodium methylate 、 silver trifluoromethanesulfonate 、 methyl orange 、 sodium hydride 、 sodium cyanoborohydride 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 6.33h， 生成 甲基 3,6-二-O-苄基-2-脱氧-2-(1,3-二氧代-1,3-二氢-2H-异吲哚-2-基)吡喃己糖苷
  参考文献：
  名称：

  Efficient Synthesis of 3,6-Dideoxy-β-d-arabino-hexopyranosyl-Terminated LacdiNac Glycan Chains of the Trichinella spiralis Parasite

  摘要：

  The synthesis of a linear trisaccharide epitope of the Trichinella spiralis N-linked glycan, in a form amenable to glycoconjugate formation, is reported. The trisaccharide contains the synthetically challenging LacdiNAc [beta-GalpNAc(1-->4)-beta-GlcpNAc] element, as well as a terminal 3,6-dideoxy-beta-D-arabino-hexopyranose (tyvelose) residue. An orthogonal protection strategy is described, which permits the protection and manipulation of three amino groups present in the disaccharide beta-GalNAc(1-->4)-beta-GlcNAc and the tether used to prepare neoglycoconjugates. The beta-linked dideoxyhexose was generated in excellent yield by the introduction of the dideoxyhexose unit as a beta-D-ribo-hexopyranoside (paratose) followed by an oxidation-reduction sequence to generate the beta-D-arabino configuration in high diastereomeric excess. The required dideoxyhexose donor was synthesized in a series of high-yielding steps from glucose utilizing the p-methoxyphenyl glycoside.

  DOI：

  10.1021/jo991812k
• 作为产物：
  描述：

  2-脱氧-2-苯二酰亚胺-1,3,4,6-四-氧-乙酰-β-D-吡喃葡萄糖 在 氢溴酸 作用下， 以 乙酸酐 、 溶剂黄146 为溶剂， 反应 2.0h， 生成 溴2-脱氧-2-N-邻苯二甲酰亚胺基-3,4,6-三-O-乙酰基-alpha,beta-D-吡喃葡萄糖苷
  参考文献：
  名称：

  Practical syntheses of B disaccharide and linear B type 2 trisaccharide—non-primate epitope markers recognized by human anti-α-Gal antibodies causing hyperacute rejection of xenotransplants

  摘要：

  Synthetic protocols are presented for the elaboration of Gal alpha1 --> 3GalOR and Gal alpha1 --> 3Gal beta1 --> 4GlcNAcOR di- and trisaccharides that use a common Gal donor/acceptor unit, and are potentially adaptable to scale-up. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(01)00196-x

文献信息

• [EN] CARBOHYDRATE-MODIFIED GLYCOPROTEINS AND USES THEREOF<br/>[FR] GLYCOPROTÉINES MODIFIÉES PAR GLUCIDE ET LEURS UTILISATIONS
  申请人：NEWLINK GENETICS CORP

  公开号：WO2014151423A1

  公开（公告）日：2014-09-25

  The present invention provides immunogenic compounds which stimulate immune responses in a subject. The present invention provides compositions comprising an isolated glycoprotein antigen covalently bound at pre-existing carbohydrate residues present on the glycoprotein to a carbohydrate epitope. The present invention also provides a method to induce an immune response in a subject comprising administering the compounds of the invention. The present invention further provides methods of making the compounds of the invention and methods of using the compounds of the invention to stimulate immune responses to infectious disease agents and tumors.

  本发明提供了刺激受试者免疫反应的免疫原化合物。本发明提供了包含一个孤立的糖蛋白抗原的组合物，该糖蛋白抗原以共价结合的方式结合在糖蛋白上已有的糖残基上，形成一个糖基表位。本发明还提供了一种诱导受试者免疫反应的方法，包括给予本发明的化合物。本发明还提供了制备本发明化合物的方法，以及利用本发明化合物刺激免疫反应以应对传染病和肿瘤的方法。
• Regio/Stereoselective Glycosylation of Diol and Polyol Acceptors in Efficient Synthesis of Neu5Ac-α-2,3-LacNPhth Trisaccharide
  作者：Ying Zhang、Fu-Long Zhao、Tao Luo、Zhichao Pei、Hai Dong

  DOI：10.1002/asia.201801486

  日期：2019.1.4

  was developed. First, the regio/stereoselective glycosylation between glycoside donors and glucoNPhth diol acceptors was investigated. It was found that the regioselectivity depends not only on the steric hindrance of the C2‐NPhth group and the C6‐OH protecting group of the glucosamine acceptors, but also on the leaving group and protecting group of the glycoside donors. Under optimized conditions, LacNPhth

  开发了Neu5Ac-α-2,3-LacNPhth三糖衍生物的简便方法。首先，研究了糖苷供体和葡萄糖NPhth二醇受体之间的区域/立体选择性糖基化。发现区域选择性不仅取决于葡糖胺受体的C2-NPhth基团和C6-OH保护基的空间位阻，还取决于糖苷供体的离去基团和保护基。在优化条件下，LacNPhth衍生物在高达92％的产率通过全乙酰-α-D-吡喃半乳糖三氯之间的区域选择性/立体选择性糖基化合成p -甲氧基苯基6- ö -叔-butyldiphenylsilyl -2-脱氧-2-苯二甲酰亚-β- d-吡喃葡萄糖苷，避免形成糖基化原酸酯和异头糖苷配基。然后，将LacNPhth衍生物脱酰基，然后通过TBDPS保护在伯位置上，以形成LacNPhth多元醇受体。最后，通过LacNPhth多元醇受体与亚磷酸唾液酸基酯供体之间的区域/立体选择性糖基化反应，以48％的产率合成了Neu5Ac-α-2,3-La
• A catalytic Koenigs-Knorr glycosylation based on acceptor activation with In(NTf2)3
  作者：Changwei Li、Haijing Liang、Zhan-xin Zhang、Zhaoyan Wang、Lan Yu、Huanxiang Liu、Fengli An、Shaohua Wang、Lixia Ma、Weihua Xue

  DOI：10.1016/j.tet.2018.05.080

  日期：2018.7

  important for gaining better insight into biological processes of significance to medicinal chemistry. Herein, we describe an In(NTf2)3 -catalyzed Koenigs-Knorr glycosylation based on the activation of an alcoholic hydroxyl group. A catalytic amount of In(NTf2)3 enables effective glycosylation of diverse alcohols with peracylated aldosyl bromides as donors, leading to the stereoselective formation of a series

  有效的糖基化方法的开发对于更好地了解对药物化学具有重要意义的生物学过程至关重要。在本文中，我们描述了基于醇羟基的活化的In（NTf 2）3催化的Koenigs-Knorr糖基化。催化量的In（NTf 2）3使用过酰基化的醛糖基溴作为供体，可以使各种醇类有效糖基化，从而以令人满意的收率立体选择性地形成一系列糖苷。该方案的特点是反应条件温和，官能团耐受性好，同时不需要任何添加剂。而且，这种转化的潜在效用通过重要的药用相关生物分子合成的便捷合成得到了证明。
• <i>N</i>-Alkyl derivatives of diosgenyl 2-amino-2-deoxy-β-D-glucopyranoside; synthesis and antimicrobial activity
  作者：Agata Walczewska、Daria Grzywacz、Dorota Bednarczyk、Małgorzata Dawgul、Andrzej Nowacki、Wojciech Kamysz、Beata Liberek、Henryk Myszka

  DOI：10.3762/bjoc.11.97

  日期：——

  Diosgenyl 2-amino-2-deoxy-β-D-glucopyranoside is a synthetic saponin exhibiting attractive pharmacological properties. Different pathways tested by us to obtain this glycoside are summarized here. Moreover, the synthesis of N-alkyl and N,N-dialkyl derivatives of the glucopyranoside is presented. Evaluation of antibacterial and antifungal activities of these derivatives indicates that they have no inhibitory activity against Gram-negative bacteria, whereas many of the tested N-alkyl saponins were found to inhibit the growth of Gram-positive bacteria and human pathogenic fungi.

  Diosgenyl 2-amino-2-deoxy-β-D-glucopyranoside是一种具有吸引人的药理特性的合成皂苷。我们测试了不同的途径来获得这种糖苷，这里总结了这些途径。此外，还介绍了合成葡萄糖吡喃糖苷的N-烷基和N,N-二烷基衍生物。对这些衍生物的抗菌和抗真菌活性评估表明，它们对革兰氏阴性菌没有抑制活性，而许多经过测试的N-烷基皂苷被发现抑制了革兰氏阳性菌和人类病原真菌的生长。
• Synthesis and characterization of some anomeric pairs of per-O-acetylated aldohexopyranosyl cyanides (per-O-acetylated 2,6-anhydroheptononitriles). On the reaction of per-O-acetylaldohexopyranosyl bromides with mercuric cyanide in nitromethane
  作者：Robert Walter Myers、Yuan Chuan Lee

  DOI：10.1016/0008-6215(84)85065-x

  日期：1984.9

  per-O-acetylaldohexopyranosyl cyanides of D-galactose, L-fucose, D-glucose, and D-mannose, as well as of 3,4,6-tri-O-acetyl-2-deoxy-2-phthalimido-beta-D-glucopyranosyl cyanide, are described. Cyanation of the readily available, per-O-acetylaldohexopyranosyl bromides with mercuric cyanide in nitromethane, and subsequent purification, gave the corresponding, crystalline glycosyl cyanides with a high degree of

  D-半乳糖，L-岩藻糖，D-葡萄糖和D-甘露糖以及3,4,6-三-O-乙酰-描述了2-脱氧-2-邻苯二甲酰亚胺基-β-D-吡喃葡萄糖基氰化物。在硝基甲烷中将氰化汞与现成的全-O-乙酰基醛基吡喃并吡喃糖基溴化物氰化，然后纯化，得到相应的结晶的糖基氰基氰化物，具有较高的1,2-反式立体选择性。因此，以20至79％的产率获得1,2-反式构型的全-O-乙酰化的醛-己二吡喃喃糖基氰化物，而以小于或等于8.4％的产率获得相应的1,2-顺式异构体。如此制备的1,2-反式：1,2-顺式端基异构体的比例大于或等于8.5：1。这些不可逆的氰化反应的主要副产物是全-O-乙酰化的1,2-O- [1-（异氰基和内氰基）亚乙基] aldohexopyranoses，得率高达40％。通过元素分析，化学转化，振动光谱以及13C和1H核磁共振光谱明确地确定了每个O-乙酰基乙二醛-吡喃并吡喃糖基氰化物的结构分配。描述了这些C