(E)-ethyl-(3-O-methyl-5,6-dideoxy-1,2-O-isopropylidene)-α-D-1,4-heptofuranosyl-5-enoate

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (E)-ethyl-(3-O-methyl-5,6-dideoxy-1,2-O-isopropylidene)-α-D-1,4-heptofuranosyl-5-enoate
• 英文别名: ethyl (E)-[3-O-methyl-5,6-dideoxy-1,2-O-isopropylidene-α-D-gluco]-heptofuran-5-en-uronate；ethyl-(5,6-dideoxy-1,2-O-isopropylidene-3-O-methyl-D-xylo-hepto-5E-enofuranosid)uronate；ethyl 1,2-O-isopropylidene-3-O-methyl-β-L-threo-hept-5-eno-furanosyluronate；ethyl (E)-3-[(3aR,5R,6S,6aR)-6-methoxy-2,2-dimethyl-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-5-yl]prop-2-enoate
• 化学式: C₁₃H₂₀O₆
• 分子量: 272.298
• InChiKey: LIMVIYAZOAEKPQ-INHSLIIYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  63.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (E)-ethyl-(3-O-methyl-5,6-dideoxy-1,2-O-isopropylidene)-α-D-1,4-heptofuranosyl-5-enoate 在 palladium on activated charcoal lithium hydroxide 、 氢气 作用下， 以 四氢呋喃 、 水 、 乙酸乙酯 为溶剂， 20.0 ℃ 、241.32 kPa 条件下， 生成 5,6-dideoxy-1,2-O-isopropylidene-3-O-methyl-D-xylofuranosiduronic acid
  参考文献：
  名称：

  An Olefin Metathesis Route for the Preparation of (1→6)-Linked C-Disaccharide Glycals. A Convergent and Flexible Approach to C-Saccharide Synthesis

  摘要：

  A convergent route to a variety of C-1-disaccharide glycals based on the olefin metathesis reaction of enol ethers and alkenes is described. The DCC-mediated coupling reaction of a variety of pentose enitols (la-c) with a number of C-5- and C-6-monosaccharide carboxylic acids (2a-e) gave the corresponding esters 3a-1 in good yield. Methylenation of these compounds was followed by ring-closing metathesis, mediated by the Schrock molybdenum catalyst 8 in warm toluene, to provide the target C-disaccharide glycals 5a-1. The formed enol ether double bond in 5a was then transformed, via standard manipulations, into a variety of C-disaccharide derivatives 21-25.

  DOI：

  10.1021/jo0005159
• 作为产物：
  描述：

  ((3aR,5R,6S,6aR)-6-Methoxy-2,2-dimethyl-tetrahydro-furo[2,3-d][1,3]dioxol-5-yl)-methanol 在 swern reagent 作用下， 以 二氯甲烷 、 二甲基亚砜 、 苯 为溶剂， 生成 (E)-ethyl-(3-O-methyl-5,6-dideoxy-1,2-O-isopropylidene)-α-D-1,4-heptofuranosyl-5-enoate
  参考文献：
  名称：

  An Olefin Metathesis Route for the Preparation of (1→6)-Linked C-Disaccharide Glycals. A Convergent and Flexible Approach to C-Saccharide Synthesis

  摘要：

  A convergent route to a variety of C-1-disaccharide glycals based on the olefin metathesis reaction of enol ethers and alkenes is described. The DCC-mediated coupling reaction of a variety of pentose enitols (la-c) with a number of C-5- and C-6-monosaccharide carboxylic acids (2a-e) gave the corresponding esters 3a-1 in good yield. Methylenation of these compounds was followed by ring-closing metathesis, mediated by the Schrock molybdenum catalyst 8 in warm toluene, to provide the target C-disaccharide glycals 5a-1. The formed enol ether double bond in 5a was then transformed, via standard manipulations, into a variety of C-disaccharide derivatives 21-25.

  DOI：

  10.1021/jo0005159

文献信息

• Unequivocal Experimental Evidence for a Unified Lithium Salt-Free Wittig Reaction Mechanism for All Phosphonium Ylide Types: Reactions with β-Heteroatom-Substituted Aldehydes Are Consistently Selective for<i>cis</i>-Oxaphosphetane-Derived Products
  作者：Peter A. Byrne、Declan G. Gilheany

  DOI：10.1021/ja300943z

  日期：2012.6.6

  erythro-β-hydroxyphosphonium salt) in reactions involving aldehydes bearing heteroatom substituents in the β-position. The effect operates with both benzaldehydes and aliphatic aldehydes and is shown not to operate in the absence of the heteroatom substituent on the aldehyde. The discovery of an effect that is common to reactions of all ylide types strongly argues for the operation of a common mechanism in all Li

  无锂盐维蒂希反应的真实过程长期以来一直是有机化学中一个有争议的问题。在此，我们报告了所有三种主要鏻叶立德类（非稳定化、半稳定化和稳定化）的 Wittig 反应所共有的实验效果：对顺式氧杂膦烷及其衍生产物（Z -烯烃和赤型-β-羟基鏻盐）在涉及在 β 位带有杂原子取代基的醛的反应中。该效应对苯甲醛和脂肪族醛都起作用，并且显示在醛上没有杂原子取代基的情况下不起作用。所有叶立德类型反应共有效应的发现有力地证明了所有 Li 无盐 Wittig 反应的共同机制。此外，结果表明，由 Vedejs 和同事提出的 [2+2] 环加成机制最容易解释，并由 Aggarwal、Harvey 和同事补充，从而为支持该机制提供了强有力的确证证据。值得注意的是，在半稳定叶立德的情况下，邻位取代基的协同作用得到证实，并被环加成机制所适应。该效应也显示在三苯基膦衍生的叶立德的反应中起作用，并且先前已在水性条件下的反应中观
• ‘Off template site’ [3+3] annulation reaction on sugar derived enal: stereoselective synthesis of C–C-linked pseudo-saccharide precursors †IICT communication no. 4167. †
  作者：G.V.M Sharma、A.Subhash Chander、Palakodety Radha Krishna、K Krishnudu、M.H.V Ramana Rao、A.C Kunwar

  DOI：10.1016/s0957-4166(00)00222-6

  日期：2000.7

  A [3+3] annulation protocol at an ‘off template’ site of a sugar-derived enal synthon is used effectively for the stereoselective synthesis of C–C-linked pseudo-saccharide precursors. The chirality is induced from the sugar synthon during the installation of carbocycle at the C-5 of sugar template.

  糖衍生的烯类合成子的“非模板”位点上的[3 + 3]环空协议可有效用于C-C连接的假糖前体的立体选择性合成。在将碳环安装在糖模板的C-5期间，由糖合成子诱导手性。
• A Versatile Protocol for theSynthesis of Oxazole and 3-Nitro/3-Carbethoxy Pyrrole<i>C</i>-Nucleosides using TOSMIC
  作者：Palakodety Radha Krishna、Vuyyuru V. Reddy、Gangavaram V. Sharma

  DOI：10.1055/s-2003-41007

  日期：——

  The synthesis of oxazole and pyrrole C-nucleosides usingTOSMIC in moderate to good yields is reported.

  据报道，使用 TOSMIC 以中等至良好的产率合成恶唑和吡咯 C-核苷。
• Synthesis of glycosylated β-amino acids as new class of antitubercular agents
  作者：R.P. Tripathi、R. Tripathi、V.K. Tiwari、Laxmi Bala、S Sinha、A. Srivastava、R. Srivastava、B.S. Srivastava

  DOI：10.1016/s0223-5234(02)01398-3

  日期：2002.9

  A series of glycosylated P-amino acids was prepared and evaluated against Mycohacterium tuberculosis, M. avium, M. fortuitum and M. smegmatis. The compounds were designed to mimic the enzyme D-alanine racemase and glycosyl transferase involved in the biosynthesis of essential cell wall peptidoglycan and arabinogalactan. Though most of the compounds exhibited little activity, however, one showed significant activity against all the strains in cell culture and activity was confirmed by BACTEC method. (C) 2002 Editions scientifiques et medicales Elsevier SAS. All rights reserved.
• Synthesis and antifilarial evaluation of N1,N n- xylofuranosylated diaminoalkanes
  作者：V.K Tiwari、N Tewari、D Katiyar、R.P Tripathi、K Arora、S Gupta、R Ahmad、A.K Srivastava、M.A Khan、P.K Murthy、R.D Walter

  DOI：10.1016/s0968-0896(03)00033-6

  日期：2003.4

  A series of N-1,N-n-xylofuranosylated diaminoalkanes (3-9 and 11-18) has been synthesized either by reductive amination of deoxy xylouloses (2a, 2b) with amines followed by one pot reduction with NaBH4 or NaCNBH3; or by 1,4-conjugate addition of amines to glycosyl olefinic esters (10a, 10b). The compounds were screened for their interference with filarial worms' glutathione metabolism, a potential target for chemotherapeutic attack. Interestingly, these compounds affected intracellular glutathione, gamma-glutamyl cysteine synthetase, glutathione reductase and glutathione-S-transferase(s) of bovine filarial worms to varying degrees. Some of the compounds though effected the motility and MTT reduction potential of filarial worms Brugia malayi, however, little microfilaricidal and macrofilaricidal were noted with compounds at 50 mg/kg oral dose. Compounds 6, 16 and 17 were evaluated also for in vivo activity. (C) 2003 Elsevier Science Ltd. All rights reserved.