(1R,4S)-2,2:3,3-bis(ethylenedioxy)-1,7,7-trimethylbicyclo[2.2.1]heptane | 24022-14-8

• 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)-2,2:3,3-bis(ethylenedioxy)-1,7,7-trimethylbicyclo[2.2.1]heptane
• 英文别名: camphorquinone bis(ethylene ketal)；(1R,4S)-2,2,3,3-bis(ethylenedioxy)-1,7,7-trimethylbicyclo[2.2.1]heptane
• CAS: 24022-14-8
• 化学式: C₁₄H₂₂O₄
• 分子量: 254.326
• InChiKey: FYCSNAKUYUMEIG-CMPLNLGQSA-N

物化性质

• 熔点：
  63-63.5 °C
• 沸点：
  320.9±37.0 °C(Predicted)
• 密度：
  1.20±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  18
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1R,4S)-2,2:3,3-bis(ethylenedioxy)-1,7,7-trimethylbicyclo[2.2.1]heptane 在 palladium on activated charcoal 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 硫酸 、 水 、 氢气 、 N,N'-二环己基碳二亚胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 乙醇 为溶剂， -78.0~20.0 ℃ 、101.33 kPa 条件下， 反应 51.25h， 生成 (1S,2R,5S,8R)-5-ethyl-8,11,11-trimethyl-3-oxa-6-azatricyclo[6.2.1.02,7]undec-6-en-4-one
  参考文献：
  名称：

  Selective Synthesis of Either Enantiomer of α-Amino Acids by Switching the Regiochemistry of the Tricyclic Iminolactones Prepared from a Single Chiral Source

  摘要：

  Preparation of L-alpha-amino acids was easily accomplished simply by exchanging the position of the lactone group of our recently reported chiral template 1 from C-2 to C-3. The new chiral template 7 was prepared in 54% overall yield over five steps from (1R)-(+)-camphor. Alkylation of iminolactone 7 afforded the alpha-monosubstituted products in good yields and excellent diastereoselectivities (>98%). Hydrolysis of the alkylated iminolactones furnished the desired L-alpha-amino acids in good yields and ee with nearly quantitative recovery of chiral auxiliary 4.

  DOI：

  10.1021/jo026285a
• 作为产物：
  描述：

  左旋樟脑 在 selenium(IV) oxide 、 依沙酰胺 、 对甲苯磺酸 作用下， 以 乙酸酐 、 苯 为溶剂， 反应 51.0h， 生成 (1R,4S)-2,2:3,3-bis(ethylenedioxy)-1,7,7-trimethylbicyclo[2.2.1]heptane
  参考文献：
  名称：

  樟脑醌试图拆分1,2-二醇的动力学拆分：（R）-（氯甲基）环氧乙烷的产生

  摘要：

  表氯醇（R）-（氯甲基）环氧乙烷是通过手性酮D-樟脑醌（1,7,7-三甲基双环[2.2.1]庚烷-2 ）由外消旋-3-氯丙烷-1,2-二醇制得的，3-dione）。这些反应导致中间体二氧戊环，其可以直接转化为氧杂环丁烷。在与溴化氢-乙酸反应之前，先用硼氢化钠还原二氧戊环中间体的C-2-酮，然后再用乙烷-1,2-二醇钠处理所得的乙酰氧基溴，即可完成这种转化。还通过D-樟脑醌与乙烷-1,2-二醇，丙烷-1,2-二醇和D-樟脑醌的反应研究了其他二氧戊环的非对映选择性形成。3，3-二甲基丁烷-1，2-二醇。

  DOI：

  10.1039/p19910000747

文献信息

• Enantioselective benzoin condensation catalyzed by spirocyclic terpene-based N-heterocyclic carbenes
  作者：Zbigniew Rafiński

  DOI：10.1016/j.tet.2016.02.049

  日期：2016.4

  The synthesis of new chiral spirocyclic triazolium salts, derived from (1S)-fenchone and (1R)-camphorquinone, are described. These salts, which are N-heterocyclic carbene precatalysts, were successfully employed in the catalytic asymmetric benzoin condensation affording acyloins with good yields and moderate enantioselectivities.

  描述了衍生自（1 S）-富琴酮和（1 R）-樟脑醌的新型手性螺环三唑鎓盐的合成。这些盐是N-杂环卡宾的预催化剂，已成功地用于催化不对称安息香缩合反应中，从而提供了具有良好收率和中等对映选择性的酰化甘油酯。
• Chiral Tricyclic Iminolactone Derived from (1<i>R</i>)-(+)-Camphor as a Glycine Equivalent for the Asymmetric Synthesis of α-Amino Acids
  作者：Peng-Fei Xu、Yuan-Shek Chen、Shu-I Lin、Ta-Jung Lu

  DOI：10.1021/jo011139a

  日期：2002.4.1

  development of a highly efficient and stereoselective methodology for the preparation of alpha-amino acids is described. The chiral template, tricyclic iminolactone 7, was synthesized from (1R)-(+)-camphor in five steps in 50% overall yield. Alkylation of iminolactone 7 afforded the alpha-monosubstituted products in good yields (74-96%) and excellent diastereoselectivities (>98%). Hydrolysis of the

  描述了用于制备α-氨基酸的高效和立体选择性方法的发展。由（1R）-（+）-樟脑分五个步骤合成手性模板三环亚氨基内酯7，总收率为50％。亚氨基内酯7的烷基化提供了高收率（74-96％）和出色的非对映选择性（> 98％）的α-单取代产物。烷基化的亚氨基内酯的水解以良好的收率和对映选择性提供了所需的α-氨基酸，并且几乎定量回收了手性助剂4。
• Asymmetric Conversion of Arenechromium Complexes to Functionalized Cyclohexenones:  Progress toward Defining an Optimum Chiral Auxiliary
  作者：Anthony J. Pearson、Alexander V. Gontcharov

  DOI：10.1021/jo971676o

  日期：1998.1.1

  the asymmetric synthesis of 5-substituted cyclohexenones via nucleophile addition to (alkoxyarene)chromium tricarbonyl complexes is described. Diastereoselectivity during the nucleophile addition step was achieved using alkoxy substituents derived from terpenoid substrates as chiral auxiliaries. Selectivities as high as 24:1 were obtained when 2-phenylisoborneol was used as the chiral auxiliary and

  描述了通过向（烷氧基芳烃）铬三羰基络合物加成亲核试剂，对5-取代的环己酮进行不对称合成的研究。使用衍生自萜类底物的烷氧基取代基作为手性助剂，可以实现亲核试剂加成步骤中的非对映选择性。当使用2-苯基异冰片醇作为手性助剂时，选择性高达24：1，而使用3,3-（亚乙基二氧基）异冰片醇则高达17：1。在将其转化成相应的环己烯醇后，主要产物的绝对立体化学由Mosher方法确定。对亲核体加成烷氧基甲苯络合物的温度依赖性的研究表明，热力学偏向邻位加成醚取代基。
• A Convenient Stereoselective Synthesis of (1<i>R</i>,2<i>S</i>,3<i>R</i>,4<i>S</i>)-3-(Neopentyloxy)isoborneol
  作者：Xavier Verdaguer、Iolanda Marchueta、Jordi Tormo、Albert Moyano、Miquel A. Pericàs、Antoni Riera

  DOI：10.1002/hlca.19980810109

  日期：1998.1.12

  A convenient preparation of (1R,2S,3R,4S)-3-(neopentyloxy)isoborneol (= (1R,2S,3R,4S)-3-(2,2-dimethyl-propoxy)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol; 1a), a valuable chiral auxiliary, is described. The synthesis involves six steps starting from the readily available camphorquinone (5) and gives 1a in 48% overall yield. The key step is the chemoselective hydrolysis of the less hindered 1,3-dioxolane

  方便制备（1 R，2 S，3 R，4 S）-3-（新戊氧基）异冰片醇（=（1 R，2 S，3 R，4 S）-3-（2,2-二甲基丙氧基）-1,7,7-三甲基双环[2.2.1]庚-2-醇；1a），一种有价值的手性助剂。从容易获得的樟脑醌（5）开始，合成过程涉及六个步骤，总产率为48％的1a。关键步骤是樟脑醌二缩醛4中受阻较少的1,3-二氧戊环部分的化学选择性水解。
• Selective Synthesis of Either Enantiomer of α-Amino Acids by Switching the Regiochemistry of the Tricyclic Iminolactones Prepared from a Single Chiral Source
  作者：Peng-Fei Xu、Ta-Jung Lu

  DOI：10.1021/jo026285a

  日期：2003.1.1

  Preparation of L-alpha-amino acids was easily accomplished simply by exchanging the position of the lactone group of our recently reported chiral template 1 from C-2 to C-3. The new chiral template 7 was prepared in 54% overall yield over five steps from (1R)-(+)-camphor. Alkylation of iminolactone 7 afforded the alpha-monosubstituted products in good yields and excellent diastereoselectivities (>98%). Hydrolysis of the alkylated iminolactones furnished the desired L-alpha-amino acids in good yields and ee with nearly quantitative recovery of chiral auxiliary 4.