(2S,3R)-2-(endo-D-galacto-pentaacetoxypentyl)-1,4-dimethyl-3-exo-nitro-7-oxabicyclo[2.2.1]hept-5-ene | 1032072-92-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (2S,3R)-2-(endo-D-galacto-pentaacetoxypentyl)-1,4-dimethyl-3-exo-nitro-7-oxabicyclo[2.2.1]hept-5-ene
• 英文别名: (2S,3R)-1',2',3',4',5'-penta-O-acetyl-1'-C-(1,4-dimethyl-3-exo-nitro-7-oxabicyclo[2.2.1]hept-5-en-2-endo-yl)-D-galactopentitol；[(2R,3S,4R,5S)-2,3,4,5-tetraacetyloxy-5-[(1R,2S,3R,4S)-1,4-dimethyl-3-nitro-7-oxabicyclo[2.2.1]hept-5-en-2-yl]pentyl] acetate
• CAS: 1032072-92-6
• 化学式: C₂₃H₃₁NO₁₃
• 分子量: 529.498
• InChiKey: KKWKYRAUOOOSTL-BOVRBPPUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  37
• 可旋转键数：
  15
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  187
• 氢给体数：
  0
• 氢受体数：
  13

反应信息

• 作为反应物：
  描述：

  甲醇 、 (2S,3R)-2-(endo-D-galacto-pentaacetoxypentyl)-1,4-dimethyl-3-exo-nitro-7-oxabicyclo[2.2.1]hept-5-ene 在 Dowex 50Wx₈-100 (H⁺) resin 作用下， 反应 120.0h， 以87%的产率得到methyl (9,10,11-tri-O-acetyl)-7-acetoxy-4,8-anhydro-1,3,6-trideoxy-5-C-methyl-6-C-nitromethyl-D-lyxo-D-galactoundec-2-ulo-2,5-furanoside
  参考文献：
  名称：

  Synthesis and ring opening reactions of 2-glyco-1,4-dimethyl-3-nitro-7-oxabicyclo[2.2.1]hept-5-enes

  摘要：

  The high-pressure asymmetric Diels-Alder reactions of D-galacto-(1a) and D-manno-3,4,5,6,7-penta-O-acetyl-1,2-dideoxy-1-nitrohept-1-enitol (1b) with 2,5-dimethylfuran (2) afforded mixtures of cycloadducts, from which the (25,3R)-3-exo-nitro (3a and 3b), (2R,3S)-3-exo-nitro (4a and 4b), and (2R,3S)-1',2',3',4',5'-penta-O-acetyl-1'-C-(1.4-dimethyl-3-endo-nitro-7-oxabicyclo[2 2 1]hept-5-en-2-exo-yl)-D-galacto-pentitol (5b) were isolated pure Deacetylanon of these compounds led to new chual mono-, b1-, and tricyclic ethers, being their asymmetric centers arising from the chiral inductor used in the cycloaddition reaction A ring opening mechanism through a 1-nitro-1,3-cyclohexadiene intermediate has been proposed (C) 2010 Elsevier Ltd All rights reserved

  DOI：

  10.1016/j.tet.2010.02.027
• 作为产物：
  描述：

  2,5-二甲基呋喃 、 3,4,5,6,7-penta-O-acetyl-1,2-dideoxy-1-nitro-D-galacto-hept-1-enitol 以 二氯甲烷 为溶剂， 20.0 ℃ 、1300.02 MPa 条件下， 反应 108.0h， 以43%的产率得到(2S,3R)-2-(endo-D-galacto-pentaacetoxypentyl)-1,4-dimethyl-3-exo-nitro-7-oxabicyclo[2.2.1]hept-5-ene
  参考文献：
  名称：

  Unexpected Reactions: From (2S,3R)-2-(endo-d-Galacto-pentaacetoxypentyl)-1,4-dimethyl-3-exo-nitro-7-oxabicyclo[2.2.1]hept-5-ene to Chiral Cyclic Ethers

  摘要：

  在高压Diels-Alder反应中，2,5-二甲基呋喃与d-galacto-3,4,5,6,7-五-O-乙酰基-1,2-去氧-1-硝基庚-1-烯醇反应，经过从粗产物中进行分馏结晶，得到纯净的(2S,3R)-2-(endo-d-galacto-五乙酰氧基戊基)-1,4-二甲基-3-exo-硝基-7-氧双环[2.2.1]庚-5-烯。其结构通过化学途径和X射线粉末衍射法确定。该加合物糖侧链的去乙酰化导致了双环体系的开环，随后发生了分子内亲核加成的串联反应，从而生成新的手性双环和三环醚。

  DOI：

  10.1055/s-2008-1042798