(Z)-N-benzyl-(3-O-benzyl-1,2-O-isopropylidene-α-D-ribofuranos-5-ylidene)amine N-oxide | 191721-03-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (Z)-N-benzyl-(3-O-benzyl-1,2-O-isopropylidene-α-D-ribofuranos-5-ylidene)amine N-oxide
• 英文别名: 1-[(3aR,5R,6R,6aR)-2,2-dimethyl-6-phenylmethoxy-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-5-yl]-N-benzylmethanimine oxide
• CAS: 191721-03-6
• 化学式: C₂₂H₂₅NO₅
• 分子量: 383.444
• InChiKey: LGGBYELCSWHSTC-DCNVXRBQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  65.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (Z)-N-benzyl-(3-O-benzyl-1,2-O-isopropylidene-α-D-ribofuranos-5-ylidene)amine N-oxide 在 碳酸氢钠 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 22.0h， 生成 (E)-5,6-didehydro-5,6-dideoxy-3-O-benzyl-1,2-O-isopropylidene-α-D-ribo-heptodialo-1,4-furanose
  参考文献：
  名称：

  Higher glycosamino acid precursors: C7 and C8 aminodialdoses via regio- and stereoselective [3+2] cycloaddition of vinyl trimethylsilane to C-glycosyl nitrones

  摘要：

  Protected C-7 and C-8 aminodialdoses were prepared stereoselectively from readily available C-5 and C-6 monosaccharide N-benzyl nitrones, by regio- and diastereoselective 1,3-dipolar cycloaddition reactions with vinyl trimethylsilane, followed by acetyl chloride-mediated cleavage of the 5-(trimethylsilyl)isoxazolidine formed. The cycloaddition reaction took place in moderate to good global yields (67-74%); estimation of diastereoselectivities from isolated yields showed total endo preference for the reaction of the D-galacto configured nitrone and high endo preference for the D-ribo analogue, but exo preference for the D-Xylo configured substrate. Attack on the re face of the nitrone was predominant in all cases. The absolute configuration of one of the protected 3-(alpha-D-galacto-pentopyranos-5-yl)isoxazolidine products was assigned by X-ray crystallographic analysis, allowing correlation of the configuration at the new stereogenic centre in the corresponding aminodialdose. For non-crystalline isoxazolidines, configurations were assigned on the basis of NOESY experiments and/or chemical correlation. Combined yields of aminodialdoses coming from isoxazolidines having identical configuration at C(3) sometimes reached high values (up to 90%). These compounds are precursors of higher-chain glycosamino acids. (C) 2002 Published by Elsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(02)00543-8
• 作为产物：
  描述：

  3-O-benzyl-1,2-O-isopropylidene-α-D-ribo-pentodialdo-1,4-furanose 、 N-苄基羟胺盐酸盐 在 sodium acetate 作用下， 以 乙醇 、 水 为溶剂， 反应 0.58h， 以74%的产率得到(Z)-N-benzyl-(3-O-benzyl-1,2-O-isopropylidene-α-D-ribofuranos-5-ylidene)amine N-oxide
  参考文献：
  名称：

  从糖硝酮制取氨基糖的新途径：6-脱氧野oji霉素的合成

  摘要：

  分别以高收率将1，3-甲基氯化镁加到由二糖衍生的硝酮3和7上，并分别得到。通过使用三氟甲磺酸三甲基甲硅烷基酯可以提高加成反应的立体选择性。N-苄基羟胺的N＝O键还原性裂解以高收率发生，并提供了容易获得的N-苄基氨基糖。这些氨基糖的潜力已通过糖苷酶抑制剂6-脱氧野oji霉素1a的合成得到证明。

  DOI：

  10.1016/s0957-4166(97)00147-x

文献信息

• A new route to aminosugars from sugar nitrones: synthesis of 6-deoxynojirimycin
  作者：Dilip D Dhavale、Vijaya N Desai、Milind D Sindkhedkar、Raghao S Mali、Carlo Castellari、Claudio Trombini

  DOI：10.1016/s0957-4166(97)00147-x

  日期：1997.5

  to dialdose derived nitrones 3 and 7 afforded and , respectively, in high yields. The stereoselectivity of the addition reaction was improved by the use of trimethylsilyl triflate. The NO bond reductive cleavages of N-benzylhydroxylamines took place in good yields and offered an easy access to N-benzylaminosugars. The potential of these aminosugars is demonstrated by the synthesis of glycosidase inhibitor

  分别以高收率将1，3-甲基氯化镁加到由二糖衍生的硝酮3和7上，并分别得到。通过使用三氟甲磺酸三甲基甲硅烷基酯可以提高加成反应的立体选择性。N-苄基羟胺的N＝O键还原性裂解以高收率发生，并提供了容易获得的N-苄基氨基糖。这些氨基糖的潜力已通过糖苷酶抑制剂6-脱氧野oji霉素1a的合成得到证明。
• Efficient synthesis of 2,6,7,8-tetrahydroxyindolizidines (castanospermine analogues) via the dipolar cycloadditions of N-benzyl-C-(tetrofuranos-4-yl)nitrones to methyl acrylate
  作者：Ma Isabel Torres-Sánchez、Pastora Borrachero、Francisca Cabrera-Escribano、Manuel Gómez-Guillén、Manuel Angulo-Álvarez、Eleuterio Álvarez、Sylvain Favre、Pierre Vogel

  DOI：10.1016/j.tetasy.2007.08.001

  日期：2007.8

  The dipolar cycloaddition of (Z) -N-benzyl-(3-O-benzy]-1,2-O-isopropylidene-alpha-D-ribofuranos-5-ylidene)amin e N-oxide to methyl acrylate gives a 53:16:26:5 diastereomeric mixture of isoxazolidine derivatives. The dipolar cycloaddition of the xylo analogue to methyl acrylate is more diastereoselective, producing a 44:13:43 mixture of only three diastereomers. The ribo-configured adducts have been converted (4 steps only) into the new (2R,6S,7S,8R,8aR)-, (2S,6S,7S,8R,8aR)-, (2S,6S,7S,8R,8aS)- and (2R,6S,7S,8R,8aS)-2,6,7,8-tetrahydroxyindolizidines. Similarly, the two xylo-configured major isoxazolidine derivatives were converted into the known derivatives (2R,6S,7R,8R,8aS)- and (2S,6S,7R,8R,8aR)-2,6,7,8-tetrahydroxyindolizidines. The six isomeric indolizidine derivatives obtained have been evaluated for their inhibiting activities towards 15 glycosidases. Only the (2R,6S,7S,8R,8aR)-configured isomer is a selective inhibitor of amyloglucosidases from Aspergillus niger (IC50 = 350 mu M) and,from Rhizopus mold (IC50 = 90 mu M, K-i = 195 mu M, non-competitive), the other indolizidines show very little inhibitory activity at 1 mM concentration. (C) 2007 Elsevier Ltd. All rights reserved.
• Regio- and stereoselective synthesis of 3- and 5-(C-glycosyl)-4-nitroisoxazolidines by nitrone–nitroalkene [3+2] cycloaddition reactions
  作者：Pastora Borrachero、Francisca Cabrera、Mª Jesús Diánez、Mª Dolores Estrada、Manuel Gómez-Guillén、Amparo López-Castro、José Mª Moreno、José L. de Paz、Simeón Pérez-Garrido

  DOI：10.1016/s0957-4166(98)00488-1

  日期：1999.1

  Cycloaddition reactions of nitrones, including sugar nitrones, with nitroalkenes, including sugar nitroolefins, led with complete regioselectivity and stereospecificity to 4,5-trans-4-nitroisoxazolidines in 51-78% global yields. The endo/exo stereoselectivity depends on the type of sugar derivative used. As expected, the best pi-diastereofacial selectivity was observed when both partners were sugar derivatives. Isomerisation of the first formed diastereomers by the action of silica gel was observed in some cases. Absolute configurations for two crystalline products were assigned by X-ray diffraction methods. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Higher glycosamino acid precursors: C7 and C8 aminodialdoses via regio- and stereoselective [3+2] cycloaddition of vinyl trimethylsilane to C-glycosyl nitrones
  作者：Pastora Borrachero、Francisca Cabrera-Escribano、Ma Jesús Diánez、Ma Dolores Estrada、Manuel Gómez-Guillén、Amparo López Castro、Simeón Pérez-Garrido、Ma Isabel Torres

  DOI：10.1016/s0957-4166(02)00543-8

  日期：2002.9

  Protected C-7 and C-8 aminodialdoses were prepared stereoselectively from readily available C-5 and C-6 monosaccharide N-benzyl nitrones, by regio- and diastereoselective 1,3-dipolar cycloaddition reactions with vinyl trimethylsilane, followed by acetyl chloride-mediated cleavage of the 5-(trimethylsilyl)isoxazolidine formed. The cycloaddition reaction took place in moderate to good global yields (67-74%); estimation of diastereoselectivities from isolated yields showed total endo preference for the reaction of the D-galacto configured nitrone and high endo preference for the D-ribo analogue, but exo preference for the D-Xylo configured substrate. Attack on the re face of the nitrone was predominant in all cases. The absolute configuration of one of the protected 3-(alpha-D-galacto-pentopyranos-5-yl)isoxazolidine products was assigned by X-ray crystallographic analysis, allowing correlation of the configuration at the new stereogenic centre in the corresponding aminodialdose. For non-crystalline isoxazolidines, configurations were assigned on the basis of NOESY experiments and/or chemical correlation. Combined yields of aminodialdoses coming from isoxazolidines having identical configuration at C(3) sometimes reached high values (up to 90%). These compounds are precursors of higher-chain glycosamino acids. (C) 2002 Published by Elsevier Science Ltd.