tert-butyldimethylsilyl 3,6-di-O-benzyl-2-deoxy-2-dimethylmaleoylamido-glucopyranoside | 216877-47-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: tert-butyldimethylsilyl 3,6-di-O-benzyl-2-deoxy-2-dimethylmaleoylamido-glucopyranoside
• 英文别名: tert-butyldimethylsilyl 3,6-di-O-benzyl-2-dimethylmaleimido-β-D-glucopyranoside；1-[(2S,3R,4R,5S,6R)-2-[tert-butyl(dimethyl)silyl]oxy-5-hydroxy-4-phenylmethoxy-6-(phenylmethoxymethyl)oxan-3-yl]-3,4-dimethylpyrrole-2,5-dione
• CAS: 216877-47-3
• 化学式: C₃₂H₄₃NO₇Si
• 分子量: 581.781
• InChiKey: CIGWPRJXLNGGFT-QWCZOQLWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.97
• 重原子数：
  41
• 可旋转键数：
  11
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  94.5
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  tert-butyldimethylsilyl 3,6-di-O-benzyl-2-deoxy-2-dimethylmaleoylamido-glucopyranoside 在 吡啶 、 三氟甲磺酸三甲基硅酯 、 四丁基氟化铵 、 溶剂黄146 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙腈 为溶剂， 反应 6.0h， 生成 benzyl 3,6-di-O-benzyl-2-deoxy-2-dimethylmaleimido-4-O-phenoxyacetyl-β-D-glucopyranosyl-(1->4)-3,6-di-O-benzyl-2-deoxy-2-dimethylmaleimido-β-D-glucopyranoside
  参考文献：
  名称：

  Synthesis of chitotetraose and chitohexaose based on dimethylmaleoyl protection

  摘要：

  tert-Butyldimethylsilyl 3,6-di-O-benzyl-2-deoxy-2-dimethylmaleimido-beta -D-glucopyranoside was readily transformed into the disaccharide glycosyl donor, 3,4,6-tri-O-acetyl-2-deoxy-2-dimethylmaleimido-beta -D-glucopyranosyl-(1 --> 4)-3,6-di-O-benzyl-2-deoxy-2-dimethylmaleimido-alpha/beta -D-glucopyranosyl trichloroacetimidate, and the disaccharide glycosyl acceptor, tert-butyldimethylsilyl 3,6-di-O-benzyl-2-deoxy-2-dimethylmaleimido-beta -D-glucopyranosyl-(1 --> 4)-3,6-di-O-benzyl-2-deoxy-2-dimethylmaleimido-beta -D-glucopyranoside. A TMSOTf-catalysed coupling of the acceptor with the donor afforded the respective tetrasaccharide derivative, which can be transformed to chitotetraose. tert-Butyldimethylsilyl 3,6-di-O-benzyl-2-deoxy-2-dimethylmaleimido-4-O-phenoxyacetyl-beta -D-glucopyranosyl-(1 --> 4)-3,6-di-O-benzyl-2-deoxy-2-dimethylmaleimido-beta -D-glucopyranoside was converted into donor 3,6-di-O-benzyl-2-deoxy-2-dimethylmaleimido-4-O-phenoxyacetyl-beta -D-glucopyranosyl- (1 --> 4)-3,6-di-O-benzyl-2-deoxy-2-dimethylmaleimido-beta -D-glucopyranosyl trichloroacetimidate. Its coupling with benzyl 3,6-di-O-benzyl-2-deoxy-2-dimethylmaleimido- beta -D-glucopyranosyl-(1 --> 4)-3,6-di-O-benzyl-2-deoxy-2-dimethylmaleimido-beta -D-glucopyranoside, followed by dephenoxyacetylation, gave benzyl 3,6-di-O-benzyl-2-deoxy-2-dimethylmaleimiido-beta -D-glucopyranosyl- (1 --> 4)-3,6-di-O-benzyl-2-deoxy-2-dimethyimaleimido-beta -D-glucopyranosyl-(1 --> 4)- 3,6-di-O-benzyl-2-deoxy-2-dimethylmaleimido- beta -D-glucopyranosyl-(1 --> 4)-3.6-di-O-benzyl-2-deoxy-2-dimethylmaleimido-beta -D-glucopyranoside, whose glycosylation furnished, after replacement of the DMM-group by the acetyl moiety and subsequent deprotection, chitohexaose. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(01)00024-6
• 作为产物：
  描述：

  2,3-二甲基马来酸酐 在 吡啶 、 咪唑 、 sodium methylate 、 sodium ethanolate 、 二正丁基氧化锡 、 一水合肼 作用下， 以 甲醇 、 乙醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 51.5h， 生成 tert-butyldimethylsilyl 3,6-di-O-benzyl-2-deoxy-2-dimethylmaleoylamido-glucopyranoside
  参考文献：
  名称：

  NOVEL COMPOSITIONS AND THERAPEUTIC METHODS

  摘要：

  本发明涉及新产品、变体、药用可接受的盐和前药，以及这些化合物的医学用途，用于治疗和/或管理败血症、败血症、脓毒性休克、眼部感染、眼部炎症、眼部血管生成、类风湿性关节炎（RA）、动脉粥样硬化、炎症性肠病（IBD）、哮喘、慢性阻塞性肺病、发热综合征、消瘦症、牛皮癣、自身免疫疾病、心脏疾病、视网膜母细胞瘤、癌症和/或任何与炎症、免疫调节和微生物感染有关的疾病。

  公开号：

  US20170281667A1

文献信息

• Synthesis of lacto-N-neotetraose and lacto-N-tetraose using the dimethylmaleoyl group as amino protective group
  作者：Mohamed R.E Aly、El-Sayed I Ibrahim、El-Sayed H El Ashry、Richard R Schmidt

  DOI：10.1016/s0008-6215(99)00051-8

  日期：1999.3

  Similarly, reaction of O-[(2,3,4,6-tetra-O-acetyl-beta- D-galactopyranosyl)-(1-->3)-4,6-O-benzylidene-2-deoxy-2-dimethylmalei mido- alpha,beta-D-glycopyranosyl] trichloroacetimidate as donor with 8 as acceptor afforded the desired tetrasaccharide benzyl (2,3,4,6-tetra-O-acetyl-beta-D- galactopyranosyl)-(1-->3)-(4,6-benzylidene-2-deoxy-2-dimethylmaleimid o- beta-D-glucopyranosyl)-(1-->3)-(2,4,6-tri-O-benz

  3）-（2,4,6-三-O-苄基-β-D-吡喃半乳糖基）-（1→4）-2,3,6-三-O-苄基-β-D-吡喃葡萄糖苷。用乙酰基取代N-二甲基马来酰基，进行O-去苄基化，最后进行O-去乙酰化，得到乳酸-N-新四糖。类似地，O-[（2,3,4,6-四-O-乙酰基-β-D-吡喃半乳糖基）-（1-> 3）-4,6-O-亚苄基-2-脱氧-2 -供体，以8为受体的-二甲基马来酸-mid，-α，β-D-甘露聚糖基]三氯乙酰亚胺酸酯，得到所需的四糖苄基（2,3,4,6-四-O-乙酰基-β-D-吡喃半乳糖基）-（1-- > 3）-（4,6-亚苄基-2-脱氧-2-二甲基马来酰亚胺邻-β-D-吡喃葡萄糖基）-（1-> 3）-（2,4,6-三-O-苄基-β- D-吡喃半乳糖基）-（1→4）-2,3,6-三-O-苄基-β-D-吡喃葡萄糖苷。除去亚苄基，用乙酰基取代N-二甲基马来酰基，然后进行O-乙酰化，得到四糖中间
• Complex Structures of Antennary Human Milk Oligosaccharides − Synthesis of a Branched Octasaccharide
  作者：Petra Knuhr、Julio Castro-Palomino、Matthias Grathwohl、Richard R. Schmidt

  DOI：10.1002/1099-0690(200111)2001:22<4239::aid-ejoc4239>3.0.co;2-m

  日期：2001.11

  blocks − 4, 7, 8, and 12 − the required three disaccharide units were obtained, resulting after further protecting group manipulation and glycoside bond formation in the desired tetrasaccharides 13 and 16. Cleavage of the TBDMS group of 13 afforded tetrasaccharide 14, which was transformed into isolactosamine-β-(13)-lactosamine trichloroacetimidate 15. Removal of the 4b,6b-O-benzylidene group of tetrasaccharide

  我们开发了一条高度收敛的合成路线，用于合成人乳八糖支链结构 β-D-吡喃半乳糖-(13)-2-乙酰氨基-2-脱氧-β-D-吡喃葡萄糖基-(13)-β- D-吡喃半乳糖基)-(14)-2-乙酰氨基-2-脱氧-β-D-吡喃葡萄糖基-(16)-[β-D-吡喃半乳糖基-(13)-2-乙酰氨基-2-脱氧-β-D-吡喃葡萄糖基-(13)]-β-D-吡喃半乳糖基-(14)-α,β-D-吡喃葡萄糖(1)。在逆合成分析中，目标结构 1 被断开为构建块 2-6。仅从四个已知的构建块 - 4、7、8 和 12 开始 - 获得所需的三个二糖单元，在所需的四糖 13 和 16 中进一步保护基团操作和糖苷键形成后得到。TBDMS 基团 13 的裂解得到四糖14，
• Synthesis of a Fragment of Bacterial Cell Wall
  作者：Dusan Hesek、Mijoon Lee、Ken-ichiro Morio、Shahriar Mobashery

  DOI：10.1021/jo035583k

  日期：2004.3.1

  Cell wall is indispensable for survival of bacteria. This large molecular "mesh" encases the entire cytoplasm of bacteria, and it is comprised of repeating backbone units of N-acetyl-glucosamine (NAG)-N-acetyl-muramic acid (NAM). A pentapeptide is attached to each of the lactyl units of the N-acetyl-muramic acid. The cell wall has both cross-linked and non-cross-linked components. In the present paper, we have devised a synthetic route for the preparation of a fragment of the cell wall comprised of a tetrasaccharide (NAG-NAM-NAG-NAM), along with the two appended peptides. We also report the syntheses of three glycosyl donors (compounds 5, 7, and 9) and three glycosyl acceptors (compounds 4, 6, and 8) based on the D-glucosamine structure as a building unit. The synthetic strategy that is disclosed is generally useful in construction of other natural products containing the D-glucosamine as a building block.