(1R,3S,4S)-3,4-Dihydro-4,5-dihydroxy-1,3-dimethyl-8-methoxy-2-benzopyran | 758695-39-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: (1R,3S,4S)-3,4-Dihydro-4,5-dihydroxy-1,3-dimethyl-8-methoxy-2-benzopyran
• 英文别名: (1R,3S,4S)-8-methoxy-1,3-dimethyl-3,4-dihydro-1H-isochromene-4,5-diol
• CAS: 758695-39-5
• 化学式: C₁₂H₁₆O₄
• 分子量: 224.257
• InChiKey: NRRHRMFXTVQERN-KEHGIVTQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  58.9
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1R,3S,4S)-3,4-Dihydro-4,5-dihydroxy-1,3-dimethyl-8-methoxy-2-benzopyran 在 silver(II) oxide 作用下， 以72%的产率得到(1R,3S,4S)-3,4-dihydro-4-hydroxy-1,3-dimethylbenzo[c]pyran-5,8-quinone
  参考文献：
  名称：

  Short, convergent, stereoselective syntheses of enantiopure 2-benzopyran-5,8-quinones related to the aphid insect pigments, the protoaphins

  摘要：

  The enantiopure (1S,3S,4R)-, (1R,3S,4S)- and (1S,3S,4S)-3,4-dihydro-1,3-dimethyl-4-hydroxy-2-benzopyrans 16, 25 and 26 are prepared in two related reaction sequences, each in eight steps and good overall yield. The starting materials are 4-methoxyphenol 6 and (2S, 1'R and 2S, 1'S)-1' ethoxyethoxypropanal 9, the latter providing the source of asymmetry from the chiral pool. The three key reactions involved in each sequence are either highly or completely diastereoselective. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2004.06.065
• 作为产物：
  描述：

  2-[(1S,2S)-2-(1-Ethoxy-ethoxy)-1-hydroxy-propyl]-4-methoxy-phenol 在 乙缩醛 、 氢氧化钾 、 camphor-10-sulfonic acid 、 水 、 四氯化钛 、 potassium carbonate 作用下， 以 甲醇 、 二氯甲烷 、 丙酮 为溶剂， 反应 10.0h， 生成 (1R,3S,4S)-3,4-Dihydro-4,5-dihydroxy-1,3-dimethyl-8-methoxy-2-benzopyran
  参考文献：
  名称：

  Short, convergent, stereoselective syntheses of enantiopure 2-benzopyran-5,8-quinones related to the aphid insect pigments, the protoaphins

  摘要：

  The enantiopure (1S,3S,4R)-, (1R,3S,4S)- and (1S,3S,4S)-3,4-dihydro-1,3-dimethyl-4-hydroxy-2-benzopyrans 16, 25 and 26 are prepared in two related reaction sequences, each in eight steps and good overall yield. The starting materials are 4-methoxyphenol 6 and (2S, 1'R and 2S, 1'S)-1' ethoxyethoxypropanal 9, the latter providing the source of asymmetry from the chiral pool. The three key reactions involved in each sequence are either highly or completely diastereoselective. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2004.06.065

文献信息

• The asymmetric synthesis of 2-benzopyrans and their quinones through intramolecular diastereoselective ring-closure of titanium phenolates of phenolic aldehydes
  作者：Robin G. F. Giles、Cynthia A. Joll

  DOI：10.1039/a901457h

  日期：——

  Treatment of the phenolic aldehyde (α′S,2S)-2-(5′-hydroxy-2′-methoxy-α′-methylbenzyloxy)propanal 15 with titanium tetraisopropoxide followed by ultrasonication led to its completely diastereoselective cyclisation in high yield to afford (1S,3S,4R)-3,4-dihydro-1,3-dimethyl-8-methoxy-2-benzopyran-4,5-diol 18, which was characterised as its more stable 4,5-diacetate 19. The diastereomeric (α′R,2S)-2-(5′-hydroxy-2′-methoxy-α′-methylbenzyloxy)propanal 17 on similar treatment gave rise to a mixture of (1R, 3S, 4R)- and (1R, 3S, 4S)-3,4-dihydro-1,3-dimethyl-8-methoxy-2-benzopyran-4,5-diols 21 and 23, isolated as the 4,5-diacetates 22 and 24, in a ratio of 3∶1. Oxidative dealkylation of the diol 18 with silver(II) oxide afforded (1S,3S,4R)-3,4-dihydro-1,3-dimethyl-4-hydroxy-2-benzopyran-5,8-quinone 2 in high yield, while the epimeric 1R quinone 40 was similarly obtained from diol 21.

  对酚醛(α′S,2S)-2-(5′-羟基-2′-甲氧基-α′-甲基苄氧基)丙醛15进行钛四异丙氧化物处理，随后进行超声波处理，导致其高产率完全读者选择性的环化，得到(1S,3S,4R)-3,4-二氢-1,3-二甲基-8-甲氧基-2-苯并吡喃-4,5-二醇18，该化合物以其更稳定的4,5-二乙酰基形式19进行表征。通过类似的方法对立体异构体(α′R,2S)-2-(5′-羟基-2′-甲氧基-α′-甲基苄氧基)丙醛17的处理，产生了(1R,3S,4R)-和(1R,3S,4S)-3,4-二氢-1,3-二甲基-8-甲氧基-2-苯并吡喃-4,5-二醇21和23的混合物，以4,5-二乙酰基形式22和24分离，比例为3∶1。用银(II)氧化物对二醇18进行氧化去烷基化，得到(1S,3S,4R)-3,4-二氢-1,3-二甲基-4-羟基-2-苯并吡喃-5,8-醌2，且以高产率得到。与此类似，从二醇21获得的表异构体1R醌40。
• Short, convergent, stereoselective syntheses of enantiopure 2-benzopyran-5,8-quinones related to the aphid insect pigments, the protoaphins
  作者：Anthony A Birkbeck、Zinka Brkic、Robin G.F Giles

  DOI：10.1016/j.tetlet.2004.06.065

  日期：2004.8

  The enantiopure (1S,3S,4R)-, (1R,3S,4S)- and (1S,3S,4S)-3,4-dihydro-1,3-dimethyl-4-hydroxy-2-benzopyrans 16, 25 and 26 are prepared in two related reaction sequences, each in eight steps and good overall yield. The starting materials are 4-methoxyphenol 6 and (2S, 1'R and 2S, 1'S)-1' ethoxyethoxypropanal 9, the latter providing the source of asymmetry from the chiral pool. The three key reactions involved in each sequence are either highly or completely diastereoselective. (C) 2004 Elsevier Ltd. All rights reserved.