(1R,2R,4R)-2-Methoxymethyl-bicyclo[2.2.1]hept-5-en-2-ol | 140850-12-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1R,2R,4R)-2-Methoxymethyl-bicyclo[2.2.1]hept-5-en-2-ol
• CAS: 140850-12-0
• 化学式: C₉H₁₄O₂
• 分子量: 154.209
• InChiKey: ZTGBVLPPODALMU-VGMNWLOBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.96
• 重原子数：
  11.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  29.46
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  甲醇 、 (1S,2S,2'R,4S)-2'-cyclohexylspiro[bicyclo[2.2.1]heptane-2,4'-[1,3]dioxolan]-5-en-5'-one 在 potassium carbonate 作用下， 反应 4.0h， 生成 (1R,2R,4R)-2-Methoxymethyl-bicyclo[2.2.1]hept-5-en-2-ol
  参考文献：
  名称：

  Enantioselective synthesis of 2-alkyl-5-methylene-1,3-dioxolan-4-ones and exo-selective Diels-Alder reactions with cyclopentadiene

  摘要：

  Highly stereoselective syntheses of chiral dienophiles (R)-1 and (R)-2 are described. Diazotization of L-serine in the presence of HCI and then treatment of the resulting beta-hydroxy-alpha-chloropropionic acid (S)-7 with KOH provides potassium glycidate ((R)-8) in good yield and high enantiomeric purity. Treatment of (R)-8 with PhSH in MeOH then provides alpha-hydroxy acid (S)-10 that can be purified by recrystallization. Condensation of (S)-10 with either pivalaldehyde or cyclohexanecarboxaldehyde followed by oxidation to the sulfone and DBU-promoted elimination of benzenesulfinic acid then provides dienophiles (R)-1 and (R)-2, respectively. Highly exo-selective Diels-Alder reactions of (R)-1 and (R)-2 with cyclopentadiene are also described. The major cycloadduct (-)-15 (94% of total) from the Diels-Alder reaction of 1 was shown to have an enantiomeric purity of greater-than-or-equal-to 99% ee. This figure defines the lower limit of enantiomeric purity of (R)-1. The diastereofacial selectivity of the Diels-Alder reactions of 1 in the exo manifold (50:1) is greater than that of 2 (20:1), as would be expected on the basis of the different steric requirements of the tert-butyl and cyclohexyl substituents of the two reagents. Consequently, dienophile 1 is the preferred reagent for complex synthetic applications, either as a chiral ketene equivalent or in contexts in which the a-hydroxy acid functionality will be preserved in the ultimate synthetic target. Finally, the possible role of dipole effects on the exo selectivity of the Diels-Alder reactions of these and related dienophiles are briefly discussed.

  DOI：

  10.1021/jo00038a028