(1R,2R,4R)-2-(hydroxymethyl)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol | 251319-25-2

• 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,2R,4R)-2-(hydroxymethyl)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol
• 英文别名: (1R,2R)-2-(hydroxymethyl)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol
• CAS: 251319-25-2
• 化学式: C₁₁H₂₀O₂
• 分子量: 184.279
• InChiKey: DDBAZKYLKGAAME-IEBDPFPHSA-N

物化性质

• 熔点：
  185-186 °C
• 沸点：
  261.6±8.0 °C(Predicted)
• 密度：
  1.069±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1R,2R,4R)-2-(hydroxymethyl)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol 在 2,2,6,6-tetramethyl-piperidine-N-oxyl 、 sodium hypochlorite 、 potassium bromide 作用下， 以 二氯甲烷 为溶剂， 以98%的产率得到(1R,2R)-2-hydroxy-1,7,7-trimethylbicyclo[2.2.1]heptane-2-carbaldehyde
  参考文献：
  名称：

  格氏试剂促进甲酰冰片和异冰片的选择性扩环和烷基化：高度取代的环戊烷的新途径

  摘要：

  甲酰基冰片，[2.2.1]-双环甲醇，与各种格氏试剂反应生成相应的烷基[3.2.1]-双环二醇，可以将其转化为新的高度取代的环戊烷，并进一步转化为3-酰基-降冰片烯。这些环膨胀-烷基化反应具有高度选择性。甲酰基异冰片醇与甲基溴化镁反应，得到仅扩环和仅烷基化的产物。

  DOI：

  10.1016/j.tetlet.2005.01.102
• 作为产物：
  描述：

  (1R,2S)-2-ethenyl-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol 在 氧气 、 臭氧 、 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 以74%的产率得到(1R,2R,4R)-2-(hydroxymethyl)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol
  参考文献：
  名称：

  Preparation of Chiral Hydroxy Carbonyl Compounds and Diols by Ozonolysis of Olefinic Isoborneol and Fenchol Derivatives: Characterization of Stable Ozonides by1H-,13C-, and17O-NMR and Electrospray Ionization Mass Spectrometry

  摘要：

  The allylic and homoallylic alcohols 1-8, prepared from (+)-camphor and (-)-fenchone, were ozonized in Et2O at -78 and treated with Et3N or LiAlH4 to give the chiral hydroxy carbonyl compounds 9-16 and the diols 17-24, respectively (Scheme I). In the case of the diols 19 and WI the formation of new chiral centers proceeded with high diastereoselectivity. These diols were prepared highly diastereoselectively also by LiAlH4 reduction of the hydroxy carbonyl compounds 11 and 16a, respectively (Scheme 2). The absolute configuration of the new chiral centers in 19 and 24 was determined by X-ray and NMR methods. The ozonization of compounds 2, 3, 7, and 8 provided the relatively stable hydroxy-substituted 1,2,4-trioxolane derivatives (ozonides) 37-40 (Scheme 5) which were characterized by H-1- and C-13-NMR spectra. ESI-MS, and natural-abundance O-17-NMR spectra.

  DOI：

  10.1002/(sici)1522-2675(19990908)82:9<1385::aid-hlca1385>3.0.co;2-y

文献信息

• Preparation and application of (+)-(3,3-dimethyl-2-methylenenorbornan-1-yl)methyl methanesulfonate: a new and versatile chiral fenchone analogue
  作者：Te-Fang Yang、Hou-Hsun Chao、Yi-Hsuan Lu、Cheng-Jung Tsai

  DOI：10.1016/j.tet.2003.08.066

  日期：2003.10

  The preparation of (+)-(3,3-dimethyl-2-methylenenorbornan-1-yl)methyl methanesulfonate (9) was carried out in 2 steps, dihydroxylation and mesylation, from (−)-2-methylenebornane. Hydrolysis and reduction of 9 gave a fenchyl alcohol (2) and a methylenefenchone (21), respectively. Oxidation of 9 afforded a new analogue (23) of the class of oxatricyclo compounds. Treatment of 9 with NBS resulted in a

  （+）-（3,3-二甲基-2-亚甲基降冰片烷-1-基）甲磺酸甲酯（9）的制备是通过（-）-2-亚甲基冰片烷的二羟基化和甲磺酰化两个步骤进行的。水解和还原9分别得到品醇（2）和亚甲基f酮（21）。9的氧化提供了一个新的类似氧杂三环化合物的类似物（23）。用NBS处理9会导致Wagner-Meerwein重排，从而生成溴化的亚甲基冰片烷衍生物（25和26），它们也是新化合物。
• Grignard reagent-promoted selective ring expansion and alkylation of formyl borneol and isoborneol: a new route to highly substituted cyclopentanes
  作者：Te-Fang Yang、Zhong-Nian Zhang、Chih-Hao Tseng、Li-Hsun Chen

  DOI：10.1016/j.tetlet.2005.01.102

  日期：2005.3

  1]-bicyclic carbinol, reacts with various Grignard reagents to produce corresponding alkyl [3.2.1]-bicyclic diols, which can be converted to new highly substituted cyclopentanes, and further to 3-acyl-bornylenes. These ring expansion–alkylation reactions are highly selective. Reaction of formyl isoborneol with methyl magnesium bromide gave ring expansion-only and alkylation-only products.

  甲酰基冰片，[2.2.1]-双环甲醇，与各种格氏试剂反应生成相应的烷基[3.2.1]-双环二醇，可以将其转化为新的高度取代的环戊烷，并进一步转化为3-酰基-降冰片烯。这些环膨胀-烷基化反应具有高度选择性。甲酰基异冰片醇与甲基溴化镁反应，得到仅扩环和仅烷基化的产物。
• Preparation of Chiral Hydroxy Carbonyl Compounds and Diols by Ozonolysis of Olefinic Isoborneol and Fenchol Derivatives: Characterization of Stable Ozonides by1H-,13C-, and17O-NMR and Electrospray Ionization Mass Spectrometry
  作者：Kalina Kostova、Vladimir Dimitrov、Svetlana Simova、Manfred Hesse

  DOI：10.1002/(sici)1522-2675(19990908)82:9<1385::aid-hlca1385>3.0.co;2-y

  日期：1999.9.8

  The allylic and homoallylic alcohols 1-8, prepared from (+)-camphor and (-)-fenchone, were ozonized in Et2O at -78 and treated with Et3N or LiAlH4 to give the chiral hydroxy carbonyl compounds 9-16 and the diols 17-24, respectively (Scheme I). In the case of the diols 19 and WI the formation of new chiral centers proceeded with high diastereoselectivity. These diols were prepared highly diastereoselectively also by LiAlH4 reduction of the hydroxy carbonyl compounds 11 and 16a, respectively (Scheme 2). The absolute configuration of the new chiral centers in 19 and 24 was determined by X-ray and NMR methods. The ozonization of compounds 2, 3, 7, and 8 provided the relatively stable hydroxy-substituted 1,2,4-trioxolane derivatives (ozonides) 37-40 (Scheme 5) which were characterized by H-1- and C-13-NMR spectra. ESI-MS, and natural-abundance O-17-NMR spectra.