2,3,4,5-di-O-isopropylidenealdehydo-L-xylose | 120522-10-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,3,4,5-di-O-isopropylidenealdehydo-L-xylose
• 英文别名: 2,3:4,5-di-O-isopropylidene-L-xylose；O²,O³;O⁴,O⁵-diisopropylidene-L-xylose；O²,O³;O⁴,O⁵-Diisopropyliden-L-xylose；(4S,5R)-5-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-1,3-dioxolane-4-carbaldehyde
• CAS: 120522-10-3
• 化学式: C₁₁H₁₈O₅
• 分子量: 230.261
• InChiKey: VFGWJIQTAFPNQZ-VGMNWLOBSA-N

物化性质

• 沸点：
  289.5±40.0 °C(Predicted)
• 密度：
  1.159±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2,3,4,5-di-O-isopropylidenealdehydo-L-xylose 在 sodium hydride 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 、 mineral oil 为溶剂， 反应 2.75h， 生成 1,2,3,4-bis-O-(1-methylethylidene)-5-O-(phenylmethyl)-5-C-2-thiazolyl-(5S)-D-xylitol
  参考文献：
  名称：

  [EN] SACCHARIDE CONJUGATES
  [FR] CONJUGUÉS SACCHARIDIQUES

  摘要：

  这项发明涉及包含糖苷共轭到成像剂或报告基团的化合物，包含它们的组合物以及使用它们的方法。具体提供了含有不同连接基团和成像剂或报告基团的BLM-二糖和BLM-单糖共轭物，用于靶向和成像肿瘤。

  公开号：

  WO2014152718A1
• 作为产物：
  描述：

  L-木糖 在 盐酸 、 mercury dichloride 、 mercury(II) oxide 作用下， 以 水 、 丙酮 为溶剂， 反应 7.25h， 生成 2,3,4,5-di-O-isopropylidenealdehydo-L-xylose
  参考文献：
  名称：

  Carbohydrate Homologation by the Use of 2-(Trimethylsilyl)thiazole. Preparative Scale Synthesis of Rare Sugars:  l-Gulose, l-Idose, and the Disaccharide Subunit of Bleomycin A₂

  摘要：

  The well established one-carbon homologation method of protected monosaccharides employing 2-(trimethylsilyl)thiazole (2-TST) as a formyl anion equivalent has been used for high yield and multigram scale synthesis of the title rare hexoses from L-xylose. Thus, L-gulose has been obtained by stereoselective anti-addition of 2-TST to aldehydo-L-xylose diacetonide followed by thiazole to formyl conversion of the resulting alcohol. The inversion of configuration at C-1 of this alcohol by an oxidation-reduction sequence prior to the aldehyde releasing from thiazole led to L-idose. The same alcohol was readily elaborated into 1,3,4,6-tetra-O-acetyl-L-gulopyranose whose highly stereoselective glycosidation coupling with 3-O-carbamoyl-2,4,6-tri-O-acetyl-alpha-D-mannosyl diethyl phosphate afforded the same peracetylated disaccharide subunit employed by Boger and Honda in the total synthesis of the antibiotic bleomycin A(2).

  DOI：

  10.1021/jo970601h

文献信息

• Convenient Synthesis of 3-Glycosylated Isocoumarins
  作者：Kasireddy Sudarshan、Indrapal Singh Aidhen

  DOI：10.1002/ejoc.201601264

  日期：2017.1.3

  A new route for the synthesis of 3-substituted and 8-hydroxy-3-substituted isocoumarins has been developed by using modified Julia olefination for initial C-C bond formation between aldehydes and benzylic-sulfones. Palladium-catalyzed Meinwald rearrangement was used as a key step for the obtainment of ketone intermediates, which on base promoted intramolecular cyclization afforded the desired isocoumarins

  通过使用改良的 Julia 烯化在醛和苄基砜之间形成初始 CC 键，开发了一种合成 3-取代和 8-羟基-3-取代异香豆素的新途径。钯催化的 Meinwald 重排被用作获得酮中间体的关键步骤，其在基础上促进了分子内环化，得到了所需的异香豆素。所开发的方法首次为迄今为止未知的 3- 糖基异香豆素和特别是其中葡糖基部分连接到异香豆素骨架的吡喃酮环的 3- 糖基异香豆素铺平了道路。
• Chromium-Mediated Stereoselective Synthesis of Carbohydrate-Derived (<i>E</i>)-α,β-Unsaturated Esters or Amides
  作者：Humberto Rodríguez-Solla、Carmen Concellón、Elena G. Blanco、Juan Ignacio Sarmiento、Pamela Díaz、Raquel G. Soengas

  DOI：10.1021/jo200548g

  日期：2011.7.1

  A chromium-mediated novel synthesis of carbohydrate-derived di- and trisubstituted (E)-α,β-unsaturated esters or amides from a range of dichloroesters or amides and a variety of sugar aldehydes is reported. The process took place with total stereoselectivity and in high yields. A mechanism based on a sequential chromium-promoted aldol-type reaction and a completely stereoselective β-elimination reaction

  据报道，铬介导的由碳水化合物衍生的二和三取代的（E）-α，β-不饱和酯或酰胺由一系列二氯酯或酰胺和各种糖醛合成。该过程以总的立体选择性和高收率进行。提出了一种基于顺序铬促进的醛醇型反应和完全立体选择性β-消除反应的机理来解释这些结果。
• Acetonation of l-pentoses and 6-deoxy-l-hexoses under kinetic control using heterogeneous acid catalysts
  作者：Jonas J. Forsman、Reko Leino

  DOI：10.1016/j.carres.2010.05.002

  日期：2010.7

  H+ proved to be an efficient catalyst for the preparation of O-isopropylidene derivatives from a series of rare sugars. Acetonation of the reducing sugars L-arabinose, L-ribose, L-xylose, L-fucose, and L-rhamnose in N,N-dimethylformamide by 2,2-dimethoxypropane or 2-methoxypropene led to the formation of the kinetically favored di-O- and/or mono-O-isopropylidene derivatives in 46-88% yields. The method

  纤维状聚合物负载的磺酸催化剂Smopex-101 H +被证明是从一系列稀有糖中制备O-异亚丙基衍生物的有效催化剂。N，N-二甲基甲酰胺中的还原糖L-阿拉伯糖，L-核糖，L-木糖，L-岩藻糖和L-鼠李糖的乙酰化作用是由2,2-二甲氧基丙烷或2-甲氧基丙烯引起的-O-和/或单-O-异亚丙基衍生物，产率为46-88％。该方法由简单的实验程序组成，不需要预先干燥的溶剂或试剂。该催化剂易于回收并且可以再生，从而使得该方法即使对于大规模合成也在经济上可行。
• Synthesis of 4-(Glycosyl)isoxazoline<i>N</i>-Oxides and Related Substances
  作者：Eisuke Kaji、Hiromi Ichikawa、Shonosuke Zen

  DOI：10.1246/bcsj.52.2928

  日期：1979.10

  4-(Glycosyl)isoxazoline N-oxides were synthesized directly from aldehydo sugars by one-step cyclization with double mole of methyl nitroacetate in a satisfactory yield. 2,3-O-Isopropylidene-D-glyceraldehyde reacted with methyl nitroacetate to give 4-(1,2-O-isopropylidene-D-glycero-dihydroxyethyl)-3,5-bis(methoxycarbonyl)isoxazoline N-oxide. The same treatment of 2,3 : 4,5-di-O-isopropylidene-aldehydo-L-arabinose

  4-(糖基)异恶唑啉N-氧化物直接由醛糖通过一步环化与双摩尔硝基乙酸甲酯以令人满意的收率合成。2,3-O-异亚丙基-D-甘油醛与硝基乙酸甲酯反应得到4-(1,2-O-异亚丙基-D-甘油-二羟乙基)-3,5-双(甲氧基羰基)异恶唑啉N-氧化物。2,3:4,5-二-O-异亚丙基-醛-L-阿拉伯糖和五-O-乙酰-醛-D-葡萄糖的相同处理也得到相应的同系物。来自相应的环状醛糖，4-醛基-3,5-双(甲氧基羰基)异恶唑啉N-氧化物，例如4-(2,3-O-异亚丙基-β-D-erythrofuranosyl)-, 4-[(4R) -3-O-苄基-1,2-O-异亚丙基-β-L-threfuranos-4-yl]-, 4-(2,3,5-tri-O-benzyl-β-D-ribofuranosyl)-,合成了 4-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl)-衍生物。
• Synthesis of Highly Functionalized Enantiopure Halocyclopropanes Derived from Carbohydrates
  作者：Humberto Rodríguez-Solla、Carmen Concellón、Vicente del Amo、Ainhoa Díaz-Pardo、Elena G. Blanco、Santiago García-Granda、M. Rosario Díaz、Ricardo Llavona、Raquel G. Soengas

  DOI：10.1002/ejoc.201300322

  日期：2013.8

  The authors acknowledge financial support from the Spanish Ministerio de Economia y Competitividad (MINECO) (grant numbers CTQ2010-14959, MAT2006-01997, MAT2010-15094 and Factoria de Cristalizacion Consolider Ingenio 2010), the Portuguese Fundacao para a Ciencia e a Tecnologia (FCT), the European Union (EU), Quadro de Referencia Estrategico Nacional (QREN), Fundo Europeu de Desenvolvimento Regional

  作者感谢西班牙政府经济与竞争部长 (MINECO)（赠款编号 CTQ2010-14959、MAT2006-01997、MAT2010-15094 和 Factoria de Cristalizacion Consolider Ingenio 2010）、葡萄牙基金（Cristalizacion Consolider Ingenio 2010）的财政支持, 欧盟 (EU), Quadro de Referencia Estrategico Nacional (QREN), Fundo Europeu de Desenvolvimento Regional (FEDER) 和 Programa Operacional Tematico Factores de Competitividade (COMPETE)（项目 PEst-C/QUI/UI0062/2011）。CC 和 V. d. A. 感谢部长级