(1R,2R)-2-hydroxybicyclo<2.2.1>hept-5-ene-2-methanol | 116697-44-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1R,2R)-2-hydroxybicyclo<2.2.1>hept-5-ene-2-methanol
• 英文别名: (1R,2R,4R)-2-(hydroxymethyl)bicyclo[2.2.1]hept-5-en-2-ol
• CAS: 116697-44-0
• 化学式: C₈H₁₂O₂
• 分子量: 140.182
• InChiKey: FZXIRIYQLOYHHX-CSMHCCOUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.31
• 重原子数：
  10.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  40.46
• 氢给体数：
  2.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  (1'S,2R,4'S,5S)-2-tert-butylspiro[1,3-dioxolane-5,5'-bicyclo[2.2.1]hept-2-ene]-4-one 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 1.0h， 以85%的产率得到(1S,2S)-2-hydroxybicyclo<2.2.1>hept-5-ene-2-methanol
  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

文献信息

• A Bifunctional Monomer Derived from Lactide for Toughening Polylactide
  作者：Feng Jing、Marc A. Hillmyer

  DOI：10.1021/ja804357u

  日期：2008.10.22

  the dienophile to prepare spiro[6-methyl-1,4-dioxane-2,5-dione-3,2'-bicyclo[2.2.1]hept[5]ene] via an exoselective and diastereofacial-selective Diels-Alder reaction. Polymerizations of this bifunctional lactide derivative were successfully carried out under ring-opening and ring-opening metathesis polymerization conditions to yield high molecular weight and high Tg polymers. We further demonstrated

  (6S)-3-Methylene-6-methyl-1,4-dioxane-2,5-dione 由 L-丙交酯合成并用作亲二烯体制备螺[6-methyl-1,4-dioxane-2, 5-dione-3,2'-bicyclo[2.2.1]hept[5]ene] 通过外选择性和非对映面选择性 Diels-Alder 反应。这种双功能丙交酯衍生物在开环和开环复分解聚合条件下成功聚合，得到高分子量和高 Tg 聚合物。我们进一步证明，通过将少量螺[6-甲基-1,4-二恶烷-2,5-二酮-3,2'-双环[2.2.1]庚[5]烯]加入聚（1， 5-环辛二烯）并将其与 DL-丙交酯共聚，可以制造出新型 PLA 聚合物合金，其韧性比 PLA 和相应的 PLA 和聚（1,5-环辛二烯）的二元共混物具有巨大的改进。
• Synthesis of Precursors of the Agalacto (<i>Exo</i>) Fragment of the Quartromicins via an Auxiliary-Controlled Exo<i>-</i>Selective Diels−Alder Reaction
  作者：Jun Qi、William R. Roush

  DOI：10.1021/ol0609208

  日期：2006.6.1

  A direct synthesis of the alpha-hydroxyaldehyde exo-5, a precursor of the exo-spirotetronate subunit of the quartromicins, was achieved through an exo-selective Lewis acid-catalyzed Diels-Alder reaction of dienophile 12a and diene 1.
• Mattay, Jochen; Mertes, Juergen; Maas, Gerhard, Chemische Berichte, 1989, vol. 122, p. 327 - 330
  作者：Mattay, Jochen、Mertes, Juergen、Maas, Gerhard

  DOI：——

  日期：——
• MATTAY, JOCHEN;MERTES, JURGEN;MAAS, GERHARD, CHEM. BER., 122,(1989) N, C. 327-330
  作者：MATTAY, JOCHEN、MERTES, JURGEN、MAAS, GERHARD

  DOI：——

  日期：——