(1R,4S,6S)-bicyclo<2.2.2>octane-6-ol-2-one | 129100-39-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1R,4S,6S)-bicyclo<2.2.2>octane-6-ol-2-one
• 英文别名: (1R,4S,6S)-6-hydroxy-bicyclo[2.2.2]octan-2-one；(1R,4S,6S)-6-hydroxybicyclo[2.2.2]octane-2-one；(1R,4S,6S)-6-hydroxybicyclo[2.2.2]octan-2-one；(-)-endo-6-Hydroxybicyclo[2.2.2]octan-2-one；(1r,4s,6s)-6-Hydroxy-bicyclo[2.2.2]octane-2-one
• CAS: 129100-39-6
• 化学式: C₈H₁₂O₂
• 分子量: 140.182
• InChiKey: NIRXVBNTTMVMMA-XVMARJQXSA-N

物化性质

• 熔点：
  197.4-199.8 °C(Solv: hexane (110-54-3); benzene (71-43-2))
• 沸点：
  268.0±23.0 °C(Predicted)
• 密度：
  1.203±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1R,4S,6S)-bicyclo<2.2.2>octane-6-ol-2-one 在 吡啶 、 potassium tert-butylate 、 三乙胺 、 lithium bromide 、 zinc(II) chloride 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， 反应 58.5h， 生成 (1R,4S,6S)-6-acetoxy-3-vinylidenebicyclo[2.2.2]octan-2-one
  参考文献：
  名称：

  Neighboring Group Participation in a Regio- and Stereoselective Chlorination of a Bicyclo[2.2.2]octanone

  摘要：

  The zinc chloride-mediated acetylation of the optically active silyl enol ether 2a gave the beta-diketone 3a (48%) together with the regio- and stereoselectively chlorinated compound 4 (27%). The yield of 4 increased to 70% by starting from the O-acetyl derivative 2c. The chlorination most likely occurs via neighboring group participation by the endo acetoxy group.

  DOI：

  10.1021/jo9607370
• 作为产物：
  描述：

  (1R,4S,6S)-6-<(tert-butyldimethylsilyl)oxy>bicyclo<2.2.2>octan-2-one 在 silver trifluoromethanesulfonate 、 乙酰氯 、 lithium diisopropyl amide 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 生成 (1R,4S,6S)-bicyclo<2.2.2>octane-6-ol-2-one
  参考文献：
  名称：

  Neighboring Group Participation in a Regio- and Stereoselective Chlorination of a Bicyclo[2.2.2]octanone

  摘要：

  The zinc chloride-mediated acetylation of the optically active silyl enol ether 2a gave the beta-diketone 3a (48%) together with the regio- and stereoselectively chlorinated compound 4 (27%). The yield of 4 increased to 70% by starting from the O-acetyl derivative 2c. The chlorination most likely occurs via neighboring group participation by the endo acetoxy group.

  DOI：

  10.1021/jo9607370

文献信息

• Asymmetric Reduction of Ketones with Catecholborane Using 2,6-BODOL Complexes of Titanium(IV) as Catalysts
  作者：Ian Sarvary、Fredrik Almqvist、Torbjörn Frejd

  DOI：10.1002/1521-3765(20010518)7:10<2158::aid-chem2158>3.0.co;2-i

  日期：2001.5.18

  Reductions performed with Ti(IV) complexes of ligands based on bicyclo[2.2.2]octane diols 5 and 6 are effective catalysts in the reduction of prochiral ketones to optically active alcohols, with catecholborane as the reducing agent. Methyl ketones are favored and enantiomeric excesses (ee) of < or =98% have been achieved with acetophenone as the substrate. Several other substrates were tested, among

  使用基于双环 [2.2.2] 辛烷二醇 5 和 6 的配体的 Ti(IV) 配合物进行的还原是将前手性酮还原为旋光醇的有效催化剂，其中儿茶酚硼烷作为还原剂。甲基酮是有利的，并且使用苯乙酮作为底物已经实现了 < 或 = 98% 的对映体过量 (ee)。测试了其他几种底物，其中包括 2-辛酮，它产生 2-辛醇，含 87% ee。检查了该方法的更多细节，例如温度、溶剂组成、分子筛 (4A) 的量和儿茶酚硼烷质量，以及配体对酸的敏感性。NMR 光谱方法用于深入了解配体和 [Ti(OiPr)4] 之间形成的配合物。为预催化剂提出了二聚体结构。
• New bicyclic γ- and δ-aminoalcohols as catalysts for the asymmetric diethylzinc addition to benzaldehyde
  作者：Cecilia Olsson、Sara Helgesson、Torbjörn Frejd

  DOI：10.1016/j.tetasy.2008.06.002

  日期：2008.6

  A new class of chiral non-racemic γ- and δ-amino alcohols based on bicyclo[2.2.1]heptane and bicyclo[2.2.2]octane have been synthesized and used as catalysts in the asymmetric diethylzinc addition to benzaldehyde.

  合成了一种基于双环[2.2.1]庚烷和双环[2.2.2]辛烷的新型手性非外消旋γ-和δ-氨基醇，并用作苯甲醛不对称二乙基锌的催化剂。
• Synthesis of Optically Active <i>endo</i>,<i>endo</i> Bicyclo[2.2.2]octane-2,5-diol, Bicyclo[2.2.2]octane-2,5-dione, and Related Compounds
  作者：Fredrik Almqvist、Niklas Ekman、Torbjörn Frejd

  DOI：10.1021/jo9601167

  日期：1996.1.1

  5S)-bicyclo[2.2.2]octane-2,5-diol ((+)-12; 98% ee) and several selectively protected optically active intermediates useful for synthetic transformations were synthesized via a 1,2-carbonyl transposition route starting from the easily available optically active (1R,4S,6S)-6-hydroxybicyclo[2.2.2]octan-2-one ((-)-2). The synthetic route also allowed the preparation of optically active (1S,4S)-bicyclo[2.2.2]octane-2

  旋光活性C（2）对称（1S，2S，4S，5S）-双环[2.2.2]辛烷-2,5-二醇（（+）-12; 98％ee）和几种选择性保护的旋光中间体有用通过容易获得的旋光性（1R，4S，6S）-6-羟基双环[2.2.2] octan-2-one（（-）-2）开始的1,2-羰基转座途径合成用于合成转化的化合物。合成路线还允许制备旋光的（1S，4S）-双环[2.2.2]辛烷-2，5-二酮（（+）-14； 98％ee）。
• An Improved Procedure for the Synthesis of Bicyclo[2.2.2]octane-2,6-dione
  作者：Fredrik Almqvist、Lars Eklund、Torbjöm Frejd

  DOI：10.1080/00397919308011243

  日期：1993.6

  Abstract Conjugate addition of Meldrum's acid to 2-cyclohexenone followed by direct cyclization in PPA/acetic acid constitutes a shorter, more reproducible and higher yielding route to bicyclo[2.2.2]octane-2,6-dione than previous methods. The crude dione could be used as substrate for the baker's yeast reduction to (1R, 4S, 6S)-bicyclo[2.2.2]octane-6-ol-2-one.

  摘要 Meldrum 酸与 2-环己烯酮的共轭加成，然后在 PPA/乙酸中直接环化，构成了比以前的方法更短、更可重现和更高产率的双环 [2.2.2] 辛烷-2,6-二酮路线。粗二酮可用作面包酵母还原为 (1R, 4S, 6S)-双环 [2.2.2] 辛烷-6-ol-2-one 的底物。
• Optically active bicyclo[2.2.2]octane derivatives; Synthesis of (1S,4R,6R)-6-hydroxybicyclo[2.2.2]octan-2-one from its enantiomer
  作者：Fredrik Almqvist、Torbjörn Freid

  DOI：10.1016/0957-4166(95)00105-x

  日期：1995.4

  (1S, 4R, 6R)-6-Hydroxybicyclo[2.2.2]octan-2-one, (+)-1, is synthesized from its enantiomer in 6 steps using a combination of orthogonal protecting groups and red-ox chemistry.

  (1S, 4R, 6R)-6-羟基双环[2.2.2]辛-2-酮，(+)-1，可采用正交保护基和氧化还原化学相结合的方法，从其对映体经6步合成得到。