ethyl 4-azido-6-O-(tert-butyldimethylsilyl)-2,3,4-trideoxy-α-D-erythro-hex-2-enopyranoside | 864852-03-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: ethyl 4-azido-6-O-(tert-butyldimethylsilyl)-2,3,4-trideoxy-α-D-erythro-hex-2-enopyranoside
• 英文别名: ethyl 4-azido-6-O-(tert-butyldimethylsilyl)-2,3,4-trideoxy-α-D-erythro-hex-2-pyranoside；6-O-tert-butyldimethylsilyl-4-azido-2,3,4-trideoxy-α-D-erythro-hex-2-enopyranoside；ethyl 4-azido-2,3,4-trideoxy-α-D-erythro-hex-2-enopyranoside；[(2S,3S,6S)-3-azido-6-ethoxy-3,6-dihydro-2H-pyran-2-yl]methoxy-tert-butyl-dimethylsilane
• CAS: 864852-03-9
• 化学式: C₁₄H₂₇N₃O₃Si
• 分子量: 313.472
• InChiKey: NLXIJPXPOWCFDX-XQQFMLRXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.0
• 重原子数：
  21
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  42
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  ethyl 4-azido-6-O-(tert-butyldimethylsilyl)-2,3,4-trideoxy-α-D-erythro-hex-2-enopyranoside 在 palladium on activated charcoal 四氧化锇 、 氢气 、 N-甲基吗啉氧化物 作用下， 以 水 、 乙酸乙酯 、 丙酮 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 反应 40.0h， 生成 ethyl 2,3-di-O-acetyl-4-amino-6-O-(tert-butyldimethylsilyl)-4-deoxy-α-D-mannopyranoside
  参考文献：
  名称：

  Stereocontrolled palladium(0)-catalyzed preparation of unsaturated azidosugars: an easy access to 2- and 4-aminoglycosides

  摘要：

  The palladium-catalyzed substitution of alkyl 4,6-di-O-acetyl-alpha-D-erythro-hex-2-eno-pyranosides using NaN3 as the nucleophile gave predominantly the corresponding alkyl 2-azido-2,3,4-trideoxy-alpha-D-threo-hex-2-enopyranosides in the presence of Pd(PPh3)(4). However, alkyl 6-O-acetyl-4-azido-2,3,4-trideoxy-alpha-D-erythro-hex-2-enopyranosi des were obtained as the major products using Pd(PPh3)4 as the catalyst in the presence of dppb as the added ligand. Conversely, alkyl 6-O-(tert-butyidimethylsilyl)-4-0-methoxycarbonyl-2,3-dideoxy-alpha-D-hex-2-enopyranosides gave exclusively alkyl 4-azido-6-O-(tert-butyldimethylsilyi)-2,3,4-trideoxy-alpha-D-erythro-hex-2-enopyranosides in the presence of Pd-2(dba)(3)/PPh3 as the catalyst and Me3SiN3 as the nucleophile. The bis-hydroxylation followed by hydrogenation of ethyl 4-azido-2,3,4-trideoxy-alpha-D-erythro-hex-2-enopyranoside afforded the corresponding 4-amino-alpha-D-mannopyranoside, when propyl 2-azido-2,3,4-trideoxy-alpha-D-threo-hex-3-enopyranoside gave the 2-amino-alpha-D-altropyranoside under the same conditions. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.06.041
• 作为产物：
  描述：

  ethyl 4,6-di-O-acetyl-2,3-dideoxy-α-D-erythrohex-2-enopyranoside 在 吡啶 、 咪唑 、 4-二甲氨基吡啶 、 tris(dibenzylideneacetone)dipalladium (0) 、 叠氮基三甲基硅烷 、 sodium methylate 、 三苯基膦 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 26.0h， 生成 ethyl 4-azido-6-O-(tert-butyldimethylsilyl)-2,3,4-trideoxy-α-D-erythro-hex-2-enopyranoside
  参考文献：
  名称：

  Stereocontrolled palladium(0)-catalyzed preparation of unsaturated azidosugars: an easy access to 2- and 4-aminoglycosides

  摘要：

  The palladium-catalyzed substitution of alkyl 4,6-di-O-acetyl-alpha-D-erythro-hex-2-eno-pyranosides using NaN3 as the nucleophile gave predominantly the corresponding alkyl 2-azido-2,3,4-trideoxy-alpha-D-threo-hex-2-enopyranosides in the presence of Pd(PPh3)(4). However, alkyl 6-O-acetyl-4-azido-2,3,4-trideoxy-alpha-D-erythro-hex-2-enopyranosi des were obtained as the major products using Pd(PPh3)4 as the catalyst in the presence of dppb as the added ligand. Conversely, alkyl 6-O-(tert-butyidimethylsilyl)-4-0-methoxycarbonyl-2,3-dideoxy-alpha-D-hex-2-enopyranosides gave exclusively alkyl 4-azido-6-O-(tert-butyldimethylsilyi)-2,3,4-trideoxy-alpha-D-erythro-hex-2-enopyranosides in the presence of Pd-2(dba)(3)/PPh3 as the catalyst and Me3SiN3 as the nucleophile. The bis-hydroxylation followed by hydrogenation of ethyl 4-azido-2,3,4-trideoxy-alpha-D-erythro-hex-2-enopyranoside afforded the corresponding 4-amino-alpha-D-mannopyranoside, when propyl 2-azido-2,3,4-trideoxy-alpha-D-threo-hex-3-enopyranoside gave the 2-amino-alpha-D-altropyranoside under the same conditions. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.06.041

文献信息

• Palladium-Catalyzed Alkynylation (Sonogashira Coupling) at C-5 of the Uracil Moiety in Modified Unsaturated Pyranosyl Nucleosides
  作者：Denis Sinou、Rajendra Srivastava、Francisco Mendonça、Janaína dos Anjos、Sebastiao de Melo

  DOI：10.1055/s-2007-965976

  日期：2007.6

  Various unsaturated 4-(5-substituted-uracil-1-yl)glycopyranosides were synthesized in good yields by a palladium-catalyzed cross-coupling reaction of ethyl 6- O-( TERT-butyldimethylsilyl)-2,3,4-trideoxy-4-[5-iodo-2,4-dioxo-3,4-dihydropyrimidin-1(2 H)-yl]-α- D- ERYTHRO-hex-2-enopyranoside with a range of acetylenic derivatives.

  以钯催化的 6-O-(叔丁基二甲基甲硅烷基)-2,3,4-三氧- 4-[5-iodo-2,4-dioxo-3,4-dihydropyrimidin-1(2 H)-yl]-α-D-ERYTHRO-hex-2-enopyranoside 与一系列炔属衍生物。
• Synthesis of Triazole-Linked Manno- and Glucopyranosyl Amino Acids
  作者：Denis Sinou、Rajendra Srivastava、Janaína dos Anjos、Sebastiao de Melo

  DOI：10.1055/s-2007-983813

  日期：2007.9

  The synthesis of two types of triazole-linked glycosyl amino acids, at C-4 and at the anomeric position for mannopyranose and glucopyranose derivatives, respectively, via a copper-catalyzed [3+2] cycloaddition of acetylenic amino acid derivatives and azide-containing glycoside is described.

  通过铜催化的炔属氨基酸衍生物和含叠氮化物的 [3+2] 环加成，分别在 C-4 和吡喃甘露糖和吡喃葡萄糖衍生物的异头位置合成两种类型的三唑连接糖基氨基酸描述了糖苷。
• Synthesis of Some Unusual (1,2,4-Oxadiazole)-Linked Hexenopyranosides and Mannopyranosides
  作者：Janaina dos Anjos、Denis Sinou、Rajendra Srivastava、Silene Carneiro do Nascimento、Sebastiao de Melo

  DOI：10.1080/07328300802120901

  日期：2008.5

  A copper-catalyzed reaction of propargyl 4,6-di-O-acetyl-2,3-dideoxy-alpha-D-erythro-hex-2-enopyranoside with 3-(4-azidophenyl)-1,2,4-oxadiazoles gave the corresponding hexenopyranosides bearing an 1,2,4-oxadiazole subunit in the aglyconic part of the molecule. The same reaction between ethyl 4-azido-2,3,4-trideoxy-alpha-D-erythro-hex-2-enopyranoside and acetylenic 1,2,4-oxadiazoles afforded the corresponding hexenopyranosides carrying a triazole and a 1,2,4-oxadiazole ring at C-4 of the carbohydrate. Combination of the two sequences gave hexenopyranosides displaying two 1,2,4-oxadiazole subunits, each one being embedded in the C-1 and C-4 frameworks, of the carbohydrate moiety. A simple dihydroxylation reaction of these unsaturated carbohydrates yielded a series of mannopyranosides bearing one or two 1,2,4-oxadiazole subunits at C-1 or C-4. These new compounds were evaluated for their cytotoxic activities against two cell strains: NCI-H-292 (lung carcinoma) and Hep-2 (larynx carcinoma), some of them presenting impressive cell growth inhibitions.
• Efficient Synthesis of Some Unsaturated [1,2,3]‐Triazole‐Linked Glycoconjugates
  作者：Ronaldo N. de Oliveira、Denis Sinou、Rajendra M. Srivastava

  DOI：10.1080/07328300600803484

  日期：2006.7

  Thermal 1,3-dipolar cycloaddition of ethyl 4-azido-2,3,4-trideoxy-alpha-D- erythro -hex-2-enopyranosides with diethyl acetylenedicarboxylate or copper-catalyzed reaction with various functionalized alkynes gave the corresponding 1-(ethyl 2,3,4-trideoxy-alpha-D- erythro -hex-2-enopyranosid-4-yl)-1 H -1,2,3-triazole derivatives in quite good yields. These unsaturated compounds could be transformed into 1-(ethyl 2,3-di-O-acetyl-4-deoxy-alpha-D-mannopyranosid-4-yl)-1 H -1,2,3-triazoles by a simple dihydroxylation reaction. Copper-catalyzed condensation of ethyl 6-O-acetyl-4-azido-2,3,4-trideoxy-alpha-D- erythro-hex-2-enopyranoside with 1,3,5-triethynylbenzene or 1,3,5-tris(prop-2-ynyloxy)benzene afforded the corresponding trivalent glycoconjugate clusters.