(1R,4S)-7,7-dimethoxybicyclo[2.2.1]heptan-2-one | 53585-72-1

• 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: (1R,4S)-7,7-dimethoxybicyclo[2.2.1]heptan-2-one
• CAS: 53585-72-1
• 化学式: C₉H₁₄O₃
• 分子量: 170.208
• InChiKey: KWYMMFHKAKFBNN-NKWVEPMBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.97
• 重原子数：
  12.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (1R,4S)-7,7-dimethoxybicyclo[2.2.1]heptan-2-one 在 盐酸 、 二异丁基氢化铝 作用下， 以 甲醇 、 正己烷 、 溶剂黄146 为溶剂， 反应 40.25h， 生成 7-norbornanone
  参考文献：
  名称：

  The octant rule. 7. Deuterium as an octant perturber

  摘要：

  DOI：

  10.1021/ja00526a038
• 作为产物：
  描述：

  7,7-二甲氧基双环(2,2,1)庚烯 在 吡啶 、 盐酸 、 sodium hydroxide 、 sodium tetrahydroborate 、 麻黄碱 、 mercury(II) diacetate 、 pyridinium chlorochromate 作用下， 反应 30.08h， 生成 (1R,4S)-7,7-dimethoxybicyclo[2.2.1]heptan-2-one
  参考文献：
  名称：

  The octant rule. 7. Deuterium as an octant perturber

  摘要：

  DOI：

  10.1021/ja00526a038

文献信息

• New Efficient Route to the Synthesis of Enantiopure (+) and (−) Bicyclo[2.2.1]heptan‐<i>syn</i>‐2,7‐diol using Lipase‐Catalyzed Transesterifications
  作者：José E. D. Martins、Luciane F. de Oliveira、Valentim E. U. Costa

  DOI：10.1080/00397910600941489

  日期：2006.11.1

  [2.2.1]hept‐5‐en‐2‐endo‐ol (±)‐7, using lipase‐catalyzed transesterification and a series of standard procedures, we prepared the enantiomers (+)‐(2R, 7S) and (−)‐(2S, 7R) bicyclo[2.2.1] heptan‐2,7‐syn‐diol 3 through a new alternative route with excellent yields and enantiomeric excess (up to 99%). These chiral bidentate compounds possess very rigid molecular structures and a favorable stereochemistry

  摘要 从外消旋的 7,7-二甲氧基-1,4,5,6-四氯双环[2.2.1]hept-5-en-2-endo-ol (±)-7 开始，使用脂肪酶催化的酯交换和一系列按照标准程序，我们通过新的替代路线制备了对映异构体 (+)-(2R, 7S) 和 (-)-(2S, 7R) bicyclo[2.2.1] heptan-2,7-syn-diol 3和对映体过量（高达 99%）。这些手性双齿化合物具有非常刚性的分子结构和有利的金属配位立体化学，因此成为不对称合成的有前途的手性配体。
• An efficient synthesis of enantiopure (+)- and (−)-syn-1,3-amino alcohols with a norbornane framework and their application in the asymmetric addition of ZnEt2 to benzaldehyde
  作者：Luciane F. de Oliveira、Valentim E.U. Costa

  DOI：10.1016/j.tetasy.2004.07.027

  日期：2004.8

  A series of new optically active (+)- and (−)-syn-1,3-amino alcohols with a norbornane framework has been synthesized. Their abilities as chiral catalysts in the enantioselective additions of ZnEt2 to benzaldehyde were evaluated. High yields and enantiomeric excesses have been achieved (up to 91%). The influence of the configuration of the carbon bearing the hydroxyl group of the ligands has been studied

  合成了具有降冰片烷骨架的一系列新的旋光性（+）-和（-）- syn -1,3-氨基醇。评估了它们在对苯甲醛中对映选择性添加ZnEt 2时作为手性催化剂的能力。已实现了高收率和对映体过量（高达91％）。已经研究了带有配体羟基的碳的构型的影响。对于观察到的对映选择性，也提出了合理的机制。
• Enzymatic resolution of endo-bicyclo[2.2.1]hept-2-yl butybates and related compounds: steric requirements in the bridge-region
  作者：K. Königsberger、K. Faber、Ch. Marschner、G. Penn、P. Baumgartner、H. Griengl

  DOI：10.1016/0040-4020(89)80096-1

  日期：1989.1

  Butyrates of endo-bicyclo(2.2.2]octanols and endo-bicyclo[2.2.1] heptan-2-ols, the latter bearing substituents of different size at C-7, were hydrolysed enzymatically using Candida cylindracea lipase. Steric factors were found to influence enantioselection: In the bicyclo [2.2.1]heptane series substrates having small substituents on C-7 were generally resolved with better enantioselection (70 to >80%

  使用Candida cylindracea脂肪酶酶促水解内双环（2.2.2）辛醇和内双环[2.2.1]庚烷-2-醇的丁酸酯，后者在C-7处具有不同大小的取代基。影响对映体的选择：在C-7上具有较小取代基的双环[2.2.1]庚烷系列底物通常比对体积大的（30-60％ee）的对映体选择（70到> 80％ee）更好。该方法为合成环戊烷和-己烷体系提供了对映体富集的结构单元。
• Synthesis of chiral norbornane derivatives as γ-amino alcohol catalysts: the effect of the functional group positions on the chirality transfer
  作者：José E.D. Martins、Clarissa M. Mehlecke、Muriell Gamba、Valentim E.U. Costa

  DOI：10.1016/j.tetasy.2006.06.029

  日期：2006.7

  Starting from (1S,4R) chiral ketone (+)-6, we developed a synthetic route to the synthesis of new chiral gamma-amino alcohols (+)- and (-)-syn-2-amino-7-hydroxy norbornane derivatives with excellent yields and enantiomeric excesses (up to 99%). These compounds were tested as chiral catalysts in the enantioselective addition of diethylzinc to benzaldehyde presenting moderate results. The results obtained, compared with others previously reported, showed that the relative disposition of the amino and hydroxyl groups on C(2) and C(7) positions, play an important role in the catalytic activity. (c) 2006 Elsevier Ltd. All rights reserved.
• An efficient synthesis of enantiopure (+)- and (−)-3-exo-amino-7,7-dimethoxynorbornan-2-exo-ols
  作者：Alexandre A.M. Lapis、Olyr C. Kreutz、Adriana R. Pohlmann、Valentim E.U. Costa

  DOI：10.1016/s0957-4166(01)00085-4

  日期：2001.3

  We describe the synthesis of new amino alcohols (+)- and (-)-3-exo-amino-7,7-dimethoxynorbonan-2-exo-ols. The (+)or (-)-7,7-dimethoxy-1,4,5,6-tetrachlorobicyclo[2.2.1]hept-5-en-2-endo-ol, obtained from the enzyme catalysed transesterification of the racemate, was reduced and dechlorinated (Na/NH3; ethanol), followed by pyridinium chlorochromate oxidation of the resultant alcohols to the corresponding ketones. After treatment with t-BuOK/BuONO, in a nitrosation reaction, alpha -keto oximes were obtained. Reduction over two steps with NaBH4 and NaBH4/NiCl2. 6H(2)O followed by in situ acetylation furnished the corresponding acetamido esters, which were hydrolysed with CH3OH/Na to produce the enantiopure amino alcohols in good yields. (C) 2001 Elsevier Science Ltd. All rights reserved.