tert-butyldimethylsilyl 4,6-O-benzylidene-2-deoxy-2-dimethylmaleoyl-β-D-glucopyranoside | 216877-67-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: tert-butyldimethylsilyl 4,6-O-benzylidene-2-deoxy-2-dimethylmaleoyl-β-D-glucopyranoside
• 英文别名: 1-[(2R,4aR,6S,7R,8R,8aS)-6-[tert-butyl(dimethyl)silyl]oxy-8-hydroxy-2-phenyl-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-7-yl]-3,4-dimethylpyrrole-2,5-dione
• CAS: 216877-67-7
• 化学式: C₂₅H₃₅NO₇Si
• 分子量: 489.641
• InChiKey: NYQBOSCMQHHCAZ-ZWALLPKMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.28
• 重原子数：
  34
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.6
• 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 4,6-O-benzylidene-2-deoxy-2-dimethylmaleoyl-β-D-glucopyranoside 在 三氟甲磺酸 、 四丁基氟化铵 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 生成 [(2R,4aR,6S,7R,8R,8aS)-7-(3,4-dimethyl-2,5-dioxopyrrol-1-yl)-2-phenyl-8-phenylmethoxy-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-6-yl] 2,2,2-trichloroethanimidate
  参考文献：
  名称：

  Synthesis of a Fragment of Bacterial Cell Wall

  摘要：

  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.

  DOI：

  10.1021/jo035583k
• 作为产物：
  描述：

  2,3-二甲基马来酸酐 在 咪唑 、 sodium methylate 、 乙酸肼 、 对甲苯磺酸 作用下， 反应 2.0h， 生成 tert-butyldimethylsilyl 4,6-O-benzylidene-2-deoxy-2-dimethylmaleoyl-β-D-glucopyranoside
  参考文献：
  名称：

  Synthesis of a Fragment of Bacterial Cell Wall

  摘要：

  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.

  DOI：

  10.1021/jo035583k

文献信息

• Linear Synthesis of a Protected H-Type II Pentasaccharide Using Glycosyl Phosphate Building Blocks
  作者：Kerry Routenberg Love、Rodrigo B. Andrade、Peter H. Seeberger

  DOI：10.1021/jo015987h

  日期：2001.11.1

  a variety of nitrogen protecting groups to ensure good glucosamine donor reactivity and protecting group compatibility. The challenge to differentiate C2 of the terminal galactose in the presence of other hydroxyl and amine protecting groups prompted us to introduce the 2-(azidomethyl)benzoyl group as a novel mode of protection for carbohydrate synthesis. The compatibility of this group with traditionally

  报道了利用糖基磷酸酯和糖基三氯乙酰亚氨酸酯结构单元线性合成完全受保护的H型II血型决定子五糖。设想了血型决定簇的自动固相合成，已证明糖基磷酸酯在逐步构建复杂的寡糖（例如H型II型抗原）中的效用。中央氨基葡萄糖结构单元的安装要求筛选各种氮保护基，以确保良好的氨基葡萄糖供体反应性和保护基的相容性。在存在其他羟基和胺保护基的情况下，区分末端半乳糖的C2的挑战促使我们引入2-（叠氮甲基）苯甲酰基作为碳水化合物合成的新型保护方式。检查了该基团与传统使用的保护基的相容性，以及其在糖基化中作为C2立体定向基团的用途。2-（叠氮甲基）苯甲酰基的应用以及对糖基供体的系统评价允许五糖的完成，并提供了预期普遍适用于血型决定簇的固相支持体合成的合成策略。
• Temporary Carbohydrate Diol Protection with Ester Groups - Orthogonality under Solid-Phase Oligosaccharide Synthesis Conditions
  作者：Shankar D. Markad、Richard R. Schmidt

  DOI：10.1002/ejoc.200900627

  日期：2009.10

  studies under SPOS conditions the glucosamine derivatives 4ab/4ba, 4ac/4ca and 4ad/4da – with Fmoc/PA, Fmoc/Lev or Fmoc/Alloc, respectively, as temporary ester protecting groups at 3-O and 4-O – were prepared. Fmoc cleavage with triethylamine in 4ab or 4ba led to PA migration, so the Fmoc/PA pair does not permit regioselective access to the vicinal hydroxy groups. Under the same reaction conditions no Lev

  对于 SPOS 条件下的区域选择性脱保护研究，氨基葡萄糖衍生物 4ab/4ba、4ac/4ca 和 4ad/4da – 分别使用 Fmoc/PA、Fmoc/Lev 或 Fmoc/Alloc 作为 3-O 和 4-O 的临时酯保护基团——准备好了。Fmoc 在 4ab 或 4ba 中用三乙胺裂解导致 PA 迁移，因此 Fmoc/PA 对不允许区域选择性地进入邻位羟基。在相同的反应条件下，没有观察到 4ac/4ca 中的 Lev 迁移或 4ad/4da 中的 Alloc 迁移。在 4ac/4ca 中用醋酸肼去除 Lev 和在 4ad/4da 中用 Pd0 和二甲酮作为亲核试剂去除 Alloc 也没有伴随 Fmoc 迁移，因此 Fmoc/Lev 对和 Fmoc/Alloc 对可以成功地用于区域选择性访问分别为 3-羟基或 4-羟基。然而，在 4ac/4ca 中用哌啶切割 Fmoc 导致 Lev 迁移，使用碱性亲核试剂进行
• 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，
• Synthetic Peptidoglycan Substrates for Penicillin-Binding Protein 5 of Gram-Negative Bacteria
  作者：Dusan Hesek、Maxim Suvorov、Ken-ichiro Morio、Mijoon Lee、Stephen Brown、Sergei B. Vakulenko、Shahriar Mobashery

  DOI：10.1021/jo035397e

  日期：2004.2.1

  The major constituent of the bacterial cell wall, peptidoglycan, is comprised of repeating units of N-acetylglucosamine (NAG) and N-acetylmuramic acid (NAM) with an appended peptide. Penicillin-binding proteins (PBPs) are involved in the final stages of bacterial cell wall assembly. Two activities for PBPs are the cross-linking of the cell wall, carried out by DD-transpeptidases, and the DD-peptidase activity, that removes the terminal D-Ala residue from peptidoglycan. The DD-peptidase activity moderates the extent of the cell wall cross-linking. There exists a balance between the two activities that is critical for the well-being of bacterial cells. We have cloned and purified PBP5 of Escherichia coli. The membrane anchor of this protein was removed, and the enzyme was obtained as a soluble protein. Two fragments of the polymeric cell wall of Gram-negative bacteria (compounds 5 and 6) were synthesized. These molecules served as substrates for PBP5. The products of the reactions of PBP5 and compounds 5 and 6 were isolated and were shown to be D-Ala and the fragments of the substrates minus the terminal D-Ala. The kinetic parameters for these enzymic reactions were evaluated. PBP5 would appear to have the potential for turnover of as many as 1.4 million peptidoglycan strands within a single doubling time (i.e., generation) of E. coli.