(1S,2S)-2-hydroxybicyclo<2.2.1>hept-5-ene-2-methanol | 82729-80-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1S,2S)-2-hydroxybicyclo<2.2.1>hept-5-ene-2-methanol
• 英文别名: (1S,2S,4S)-2-(hydroxymethyl)bicyclo[2.2.1]hept-5-en-2-ol
• CAS: 82729-80-4
• 化学式: C₈H₁₂O₂
• 分子量: 140.182
• InChiKey: FZXIRIYQLOYHHX-XLPZGREQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1S,2S)-2-hydroxybicyclo<2.2.1>hept-5-ene-2-methanol 在 sodium periodate 、 potassium dihydrogenphosphate 作用下， 以 四氢呋喃 为溶剂， 生成 (-)-(1S,4S)-bicyclo[2.2.1]hept-5-en-2-one
  参考文献：
  名称：

  设计用于与 α-酰氧基丙烯醛的对映选择性 Diels-Alder 反应的有机催化剂

  摘要：

  我们已经实现了第一个对映选择性有机催化 Diels-Alder 反应，α 取代的丙烯醛，例如 α-酰氧基丙烯醛，不仅是环状二烯，还包括无环二烯。α-酰氧基丙烯醛可用作α-卤代丙烯醛的合成等价物。本催化剂可由五氟苯磺酸(2.5-3.0当量)和衍生自Hl-Phe-1-Leu-N(CH2CH2)2的手性三胺(1当量)原位制备。5-(苄氧基甲基)环戊二烯、环戊二烯、环己二烯、2,3-二甲基丁二烯和异戊二烯与α-(对甲氧基苯甲酰氧基)丙烯醛在上述手性铵盐(2.5-20 mol %)催化下的对映选择性Diels-Alder反应-20-22 摄氏度产生相应的加合物，分别为 83、83、91、92 和 88% ee。

  DOI：

  10.1021/ja053368a
• 作为产物：
  描述：

  (-)-(1S,2S,4S)-2-formylbicyclo[2.2.1]hept-5-en-2-yl cyclohexanecarboxylate 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 生成 (1S,2S)-2-hydroxybicyclo<2.2.1>hept-5-ene-2-methanol
  参考文献：
  名称：

  手性1,1'-联萘-2,2'-二铵盐催化剂，用于与α-酰氧基丙烯醛的对映选择性Diels-Alder反应。

  摘要：

  [反应：见正文]手性1,1'-联萘-2,2'-二胺和三氟甲磺酰亚胺（Tf（2）NH）的二铵盐对于α-酰氧基丙烯醛与Diels-Alder反应具有优异的催化活性和对映选择性。环状二烯。例如，在5mol％的铵催化剂存在下，α-（环己烷羰氧基）丙烯醛与环戊二烯的Diels-Alder反应在-75℃下在EtCN中进行，以88％的收率得到加合物，其中exo为92％。 91％ee。通过混合市售的手性二胺和Tf（2）NH，可以很容易地就地制备该催化剂。

  DOI：

  10.1021/ol060490l

文献信息

• Chiral Primary Amine-Polyoxometalate Acid Hybrids as Asymmetric Recoverable Iminium-Based Catalysts
  作者：Jiuyuan Li、Xin Li、Pengxin Zhou、Long Zhang、Sanzhong Luo、Jin-Pei Cheng

  DOI：10.1002/ejoc.200900594

  日期：2009.9

  acid–base assembly of multidentate chiral primary amines and solid polyacids is presented. A suitable structurally distinctive C2-symmetric chiral primary amine (CPA) was identified in this study and the optimal CPA–POM hybrid obtained catalyzed the Diels–Alder cycloaddition of α-substituted acroleins in high yields and fair-to-high selectivity under aqueous conditions. The primary amine in the metal–organic-framework

  提出了一种通过多齿手性伯胺和固体多元酸的酸碱组装固定亚胺有机催化剂的新策略。在本研究中确定了一种合适的结构独特的 C2 对称手性伯胺 (CPA)，获得的最佳 CPA-POM 杂化物在水性条件下以高产率和公平到高的选择性催化 α-取代丙烯醛的 Diels-Alder 环加成反应. 类金属有机骨架 (MOF) 催化剂中的伯胺充当催化中心和多齿碱性中心，而磷钨酸则充当催化剂锚和活性和立体选择性调节剂的双重作用。此外，类 MOF 催化剂表现出高反应性和物理稳定性，因此可以回收和重复使用 6 次，而活性和选择性损失很小。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
• 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。
• Enantioselective Diels–Alder Reaction of α-Acyloxyacroleins Catalyzed by Chiral 1,1′-Binaphthyl-2,2′-diammonium Salts
  作者：Akira Sakakura、Kenji Suzuki、Kazuaki Ishihara

  DOI：10.1002/adsc.200600322

  日期：2006.11

  activity and enantioselectivity for the Diels–Alder reaction of α-acyloxyacroleins. For example, in the presence of 5 mol % of 2a and 9.5 mol % of Tf2NH, the Diels–Alder reaction of α-(cyclohexanecarbonyloxy)acrolein with cyclopentadiene proceeded in EtCN at −75 °C to give the adducts in 88 % yield with 92 % exo and 91 % ee. The electron-donating property of the acyl group of the α-acyloxyacroleins increases

  手性1,1'-联萘-2,2'-二胺（2a）和三氟甲磺酰亚胺（Tf 2 NH）的二铵盐对α-酰氧基丙烯醛的Diels-Alder反应显示出优异的催化活性和对映选择性。例如，在5 mol％的2a和9.5 mol％的Tf 2 NH存在下，α-（环己烷羰氧基）丙烯醛与环戊二烯的Diels-Alder反应在-75°C的EtCN中进行，得到88％的加合物。产率为92％的exo和91％的ee。α-酰氧基丙烯醛的酰基的供电子性提高了对映选择性，这是由于在过渡状态下酰基与铵基的质子之间形成了强分子内氢键。通过将可商购的手性二胺和Tf 2 NH混合，可以容易地就地制备该催化剂。
• 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.
• Enantioselective synthesis of 2-alkyl-5-methylene-1,3-dioxolan-4-ones and exo-selective Diels-Alder reactions with cyclopentadiene
  作者：William R. Roush、Bradley B. Brown

  DOI：10.1021/jo00038a028

  日期：1992.6

  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.