methylene bis(3,3'-(6,6-dimethylbicyclo(3.1.1)heptan-2-one)) | 157059-20-6

• 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: methylene bis(3,3'-(6,6-dimethylbicyclo(3.1.1)heptan-2-one))
• 英文别名: (1R,5S)-3-[[(1R,5S)-6,6-dimethyl-2-oxo-3-bicyclo[3.1.1]heptanyl]methyl]-6,6-dimethylbicyclo[3.1.1]heptan-2-one
• CAS: 157059-20-6
• 化学式: C₁₉H₂₈O₂
• 分子量: 288.43
• InChiKey: NDCIIKPZEKIQGR-VYUINMPDSA-N

物化性质

• 沸点：
  394.3±15.0 °C(predicted)
• 密度：
  1.053±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  methylene bis(3,3'-(6,6-dimethylbicyclo(3.1.1)heptan-2-one)) 在 乙酸铵 、 溶剂黄146 作用下， 反应 3.0h， 以0.80 g的产率得到(2R,4R,5R,7R)-2,4:5,7-bis-methano-3,3,6,6-tetramethyl-1,2,3,4,5,6,7,8-octahydroacridine
  参考文献：
  名称：

  Chiral pyridine N-oxides derived from monoterpenes as organocatalysts for stereoselective reactions with allyltrichlorosilane and tetrachlorosilane

  摘要：

  The synthesis of enantiomerically pure C-2-symmetric dipyridylmethane ligands and related N,N'-dioxides is reported. A procedure for the synthesis of a few new enantiomerically pure C-2-symmetric pyridine N-oxides and the preparation of four pyridine N-oxides with oxygen and nitrogen atoms as further coordinating elements in the heterocycle framework is described. All compounds were prepared from naturally occurring monoterpenes. These new compounds were assessed as organocatalysts in two different reactions, namely the allylation of aldehydes with allyltrichlorosilane that afforded homoallylic alcohols in good yields and up to 85% ee and the stilbene oxide opening by the addition of tetrachlorosilane that gave chlorohydrin in quantitative yield and up to 70% ee. (C) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2008.05.105
• 作为产物：
  描述：

  (1R)-(+)-诺蒎酮 、 (1R,5R)-6,6-dimethyl-3-methylenebicyclo[3.1.1]heptan-2-one 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 生成 methylene bis(3,3'-(6,6-dimethylbicyclo(3.1.1)heptan-2-one))
  参考文献：
  名称：

  Chiral pyridine N-oxides derived from monoterpenes as organocatalysts for stereoselective reactions with allyltrichlorosilane and tetrachlorosilane

  摘要：

  The synthesis of enantiomerically pure C-2-symmetric dipyridylmethane ligands and related N,N'-dioxides is reported. A procedure for the synthesis of a few new enantiomerically pure C-2-symmetric pyridine N-oxides and the preparation of four pyridine N-oxides with oxygen and nitrogen atoms as further coordinating elements in the heterocycle framework is described. All compounds were prepared from naturally occurring monoterpenes. These new compounds were assessed as organocatalysts in two different reactions, namely the allylation of aldehydes with allyltrichlorosilane that afforded homoallylic alcohols in good yields and up to 85% ee and the stilbene oxide opening by the addition of tetrachlorosilane that gave chlorohydrin in quantitative yield and up to 70% ee. (C) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2008.05.105

文献信息

• A new “5+1” route to arenes. Application to the facile synthesis of D4-symmetric chiral porphyrins
  作者：John Barry、Thomas Kodadek

  DOI：10.1016/s0040-4039(00)77145-0

  日期：1994.4

  A new synthesis of D4-symmetric porphyrins is presented which provides chiral macrocycles in only five steps starting from optically active cyclic ketones. The efficacy of this approach is demonstrated with the synthesis of a new porphyrin derived from R-(+)-nopinone. The development of this flexible and general route should speed the development of porphyrin-based asymmetric catalysts.

  提出了一种新的D 4-对称卟啉合成方法，该方法从旋光活性的环酮开始，仅需五个步骤即可提供手性大环。这种方法的有效性通过合成一种新的源自R-（+）-nopinone的卟啉来证明。这种灵活而通用的路线的开发应加快基于卟啉的不对称催化剂的开发。
• Synthesis and catalytic epoxidation activity of terpene-derived D4-symmetric metalloporphyrins
  作者：John F. Barry、Lara Campbell、Dudley W. Smith、Thomas Kodadek

  DOI：10.1016/s0040-4020(97)00470-5

  日期：1997.6

  We report here a flexible synthesis of chiral, D4-symmetric porphyrins from cyclic ketone starting materials. Two porphyrins have been synthesized from the terpene 1-R-(+)-nopinone, obviating the need to perform a resolution. The chloromanganese derivative of one of these porphyrins is a good catalyst for the epoxidation of terminal alkenes, providing epoxides with e.e.'s of 70% with high turnover

  我们在这里报告了从环状酮原料中灵活合成手性D 4对称卟啉的方法。从萜烯1-R-（+）-nopinone合成了两种卟啉，无需进行拆分。这些卟啉之一的氯锰衍生物是末端烯烃环氧化的良好催化剂，可提供具有70％ee的ee和高周转率的环氧化物。讨论了手性口袋中氧原子转移的预测模型。
• Chiral pyridine N-oxides derived from monoterpenes as organocatalysts for stereoselective reactions with allyltrichlorosilane and tetrachlorosilane
  作者：Giorgio Chelucci、Salvatore Baldino、Gerard A. Pinna、Maurizio Benaglia、Laura Buffa、Stefania Guizzetti

  DOI：10.1016/j.tet.2008.05.105

  日期：2008.8

  The synthesis of enantiomerically pure C-2-symmetric dipyridylmethane ligands and related N,N'-dioxides is reported. A procedure for the synthesis of a few new enantiomerically pure C-2-symmetric pyridine N-oxides and the preparation of four pyridine N-oxides with oxygen and nitrogen atoms as further coordinating elements in the heterocycle framework is described. All compounds were prepared from naturally occurring monoterpenes. These new compounds were assessed as organocatalysts in two different reactions, namely the allylation of aldehydes with allyltrichlorosilane that afforded homoallylic alcohols in good yields and up to 85% ee and the stilbene oxide opening by the addition of tetrachlorosilane that gave chlorohydrin in quantitative yield and up to 70% ee. (C) 2008 Elsevier Ltd. All rights reserved.