bis((1R,2S,5R)-2-isopropyl-5-methylcyclohexyl) (1R,2S,3S,4S)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate | 109005-04-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: bis((1R,2S,5R)-2-isopropyl-5-methylcyclohexyl) (1R,2S,3S,4S)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate
• 英文别名: bis[(1R,2S,5R)-5-methyl-2-propan-2-ylcyclohexyl] (1S,2S,3S,4R)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate
• CAS: 109005-04-1
• 化学式: C₂₉H₄₆O₄
• 分子量: 458.682
• InChiKey: BVQYOJFRQWRPGV-LOMSNOTCSA-N

物化性质

• 熔点：
  80-82 °C
• 沸点：
  526.0±50.0 °C(Predicted)
• 密度：
  1.05±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8
• 重原子数：
  33
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  bis((1R,2S,5R)-2-isopropyl-5-methylcyclohexyl) (1R,2S,3S,4S)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate 在 sodium hydroxide 作用下， 以 乙醇 为溶剂， 反应 12.0h， 以46%的产率得到(1R,2S,3S,4S)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid
  参考文献：
  名称：

  Enantioselective Diels-Alder reactions: novel constrained bis(oxazoline) ligand-metal triflate catalysts

  摘要：

  Five chiral 1,4-bis(oxazoline) ligands, each bearing a bicyclic backbone, were prepared and examined in Mg(OTf)(2)-, Zn(OTf)(2)-, and Cu(OTf)(2)-catalyzed Diels-Alder reactions. The cycloadditions were carried out at room temperature and afforded enantiomeric excess up to 88%. Surprisingly, a non-C-2-symmetric bis(oxazoline) bearing a meso backbone was among the more efficient ligands examined. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(97)00323-6
• 作为产物：
  描述：

  L-薄荷醇 在 硫酸 、 氯化二乙基铝 作用下， 以 正己烷 、 甲苯 为溶剂， 反应 1.0h， 生成 bis((1R,2S,5R)-2-isopropyl-5-methylcyclohexyl) (1R,2S,3S,4S)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate
  参考文献：
  名称：

  模块化和不对称篮子的对映选择性构造

  摘要：

  定制的A、B和C构建块的逐步 Suzuki-Miyaura 耦合提供了ABC篮子。这种对映选择性和模块化结构允许选择腔体非极性袋的深度和形状，同时还可以在边缘选择所需的官能团。建立更有效的生物受体和催化剂模拟物是触手可及的。

  DOI：

  10.1002/anie.202110849

文献信息

• Preparation and Structural Analysis of Several New α,α,α′,α′-Tetraaryl-1,3-dioxolane-4,5-dimethanols (TADDOL's) and TADDOL analogs, their evaluation as titanium ligands in the enantioselective addition of methyltitanium and diethylzinc reagents to benzald
  作者：Yoshio N. Ito、Xavier Ariza、Albert K. Beck、Andrej Boháč、Camille Ganter、Robert E. Gawley、Florian N. M. Kühnle、Juraj Tuleja、Yan Ming Wang、Dieter Seebach

  DOI：10.1002/hlca.19940770802

  日期：1994.12.14

  Preparation and screening of twenty new ligands, all analogs of α,α,α′,α′-tetraaryl-1,3-dioxolane-4,5-dimethanol (TADDOL), for the Ti-catalyzed asymmetric addition of methyltri(isopropoxy)titanium and diethylzinc to benzaldehyde are described. These ligands have the dioxolane ring of the TADDOL's replaced by cyclobutane, cyclopentane, cyclohexene, cyclohexane, bicyclo[2.2.1]heptene and -heptane and

  Ti催化不对称加成甲基三（异丙氧基）的二十种新配体的制备和筛选，这些配体是α，α，α'，α'-四芳基-1,3-二氧戊环-4,5-二甲醇（TADDOL）的所有类似物描述了钛和二乙基锌与苯甲醛。这些配体具有被环丁烷，环戊烷，环己烯，环己烷，双环[2.2.1]庚烯和-庚烷以及双环[2.2.2]辛烯和-辛烷部分取代的TADDOL的二氧戊环。一些具有取代芳基的H原子或烷基，并且其中九个具有C 2对称性。X射线晶体学和分子力学用于分析配体的结构，并且两个结构特征似乎与选择性相关：（i）螯合O原子和邻位原子的扭转角轴向Ph族的-C原子（小，约19°，最佳角度，图8），以及（ii）轴向Ph族的“垂直度”（图9）。竞争实验表明，TADDOL 1a催化甲基钛和二乙基锌的添加速度比相关的二氧戊环类似物12a，12c和12e快50倍以上（方案7），表明配体需要轴向和赤道芳基（见脚注6）这些反应的加速催化。提出了完
• Preparation of ecological catalysts derived from Zn hyperaccumulating plants and their catalytic activity in Diels–Alder reaction
  作者：Vincent Escande、Tomasz K. Olszewski、Claude Grison

  DOI：10.1016/j.crci.2013.09.009

  日期：2014.7

  Résumés Anglais Français Zn hyperaccumulating plants Noccaea caerulescens and Anthyllis vulneraria were used as the starting material for preparation of novel Lewis ecological catalysts. Those catalysts efficiently mediate the Diels–Alder reaction. High yields, very good regio- and diastereoselectivity, low catalyst loading and the possibly of its recovery and reuse, along with mild reaction conditions, eco-friendly treatment and short reaction time, are the key advantages of the presented approach. Les plantes hyperaccumulatrices de Zn Noccaea caerulescens et Anthyllis vulneraria ont été utilisées comme matières premières pour la préparation de nouveaux catalyseurs écologiques de type acides de Lewis. Ces catalyseurs ont montré une haute efficacité dans la réaction de Diels–Alder. Les avantages clés de l’approche présentée sont les suivants : rendements élevés, très bonnes régio- et diastéréosélectivités, faibles charges catalytiques, possibilité de recyclage du catalyseur, conditions réactionnelles modérées, traitement éco-compatible et courtes durées de réaction.

  摘要 英法以锌高积累植物 Noccaea caerulescens 和 Anthyllis vulneraria 为起始材料，制备了新型路易斯生态催化剂。这些催化剂能有效介导 Diels-Alder 反应。高产率、极好的区域和非对映选择性、低催化剂负载、可回收和重复使用，以及温和的反应条件、环保处理和较短的反应时间，是该方法的主要优点。 以 Zn 超积累植物 Noccaea caerulescens 和 Anthyllis vulneraria 为原料，制备了新型环保路易斯酸催化剂。这些催化剂在 Diels-Alder 反应中表现出很高的效率。该方法的主要优点如下：产率高、具有很好的区域和非对映选择性、催化剂负载量低、催化剂可回收利用、反应条件温和、生态兼容处理和反应时间短。
• Diastereoselectivities in the diels-alder reactions of cyclopentadiene with optically active dimenthyl fumarate and menthyl methyl fumarate in LiClO4/ether and on Al2O3
  作者：Satinder Bains、Richard M. Pagni、George W. Kabalka、Catherine Pala

  DOI：10.1016/s0957-4166(00)86236-9

  日期：1994.5

  Reactions of cyclopentadiene with (-)-dimenthyl fumarate, which yield adducts 1 and 2, and with (-)-menthyl methyl fumarate, which yield adducts 3 through 6, were carried out on alumina activated at different temperatures, in LiClO4/ether solutions, and in other media. Various diastereoselectivities - 2:1, 3:4, 6:5, endo:exo [(3+4):(5+6)], and % de [(3+6) - (4+5)]/[3+4+5+6] x 100] - were determined for these reactions. The LiClO4 data were analyzed using a model in which LiClO4 reversibly binds to the dienophile, resulting in competing catalyzed and uncatalyzed Diels-Alder reactions. Even in approximately 5 M LiClO4, there are sizable contributions from uncatalyzed reactions in all cases. Extrapolation of the data to infinite LiClO4, concentration yields data for the catalyzed reactions alone; only modest diastereoselectivities are seen for the catalyzed reactions. The alumina results were unusual because the endo:exo ratios of adducts were large but % de's were small. The selectivities on alumina could not be correlated to the activity of the solid. This behavior will occur when varying numbers and types of catalytic sites are exposed to the surface on activation.
• A chemical, spectroscopic, and theoretical assessment of the Lewis acidity of lithium perchlorate in diethyl ether
  作者：Richard M. Pagni、George W. Kabalka、Satinder Bains、Miechelle Plesco、Jennifer Wilson、John Bartmess

  DOI：10.1021/jo00063a037

  日期：1993.5

  Moderate diastereoselectivity is observed in the reaction of cyclopentadiene with dimethyl maleate and optically active dimenthyl fumarate in LiClO4/diethyl ether. Moderate regioselectivity is also seen in the reaction of isoprene and methyl acrylate in the same medium. NMR experiments and MNDO calculations, in conjunction with published work on Li+ in the gas phase, demonstrate that the strong, intrinsic Lewis acidity of Li+ is moderated in ether by complexation to the solvent and the counterion.
• A Selective Partial Hydrolysis of Dimenthyl Ester Using Dry Tetrabutylammonium Hydroxide
  作者：Tomoyuki Hasegawa

  DOI：10.1055/s-1999-2529

  日期：1999.1