(1R,2S)-2-exo-hydroxy-2-endo-(2-methylallyl)-1,7,7-trimethylbicyclo<2.2.1>heptane | 162302-47-8

• 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,2S)-2-exo-hydroxy-2-endo-(2-methylallyl)-1,7,7-trimethylbicyclo<2.2.1>heptane
• 英文别名: (1R,2S)-1,7,7-trimethyl-2-(2-methylprop-2-enyl)bicyclo[2.2.1]heptan-2-ol；(1R,2S)-(+)-1,7,7-trimethyl2-(2-methylallyl)bicyclo[2.2.1]heptan-2-ol；(1R,2S,4R)-1,7,7-trimethyl-2-(2-methylprop-2-enyl)bicyclo[2.2.1]heptan-2-ol
• CAS: 162302-47-8
• 化学式: C₁₄H₂₄O
• 分子量: 208.344
• InChiKey: WRCNWVSBACVXOI-MRVWCRGKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (1R,2S)-2-exo-hydroxy-2-endo-(2-methylallyl)-1,7,7-trimethylbicyclo<2.2.1>heptane 在 氧气 、 臭氧 、 三乙胺 作用下， 以 乙醚 为溶剂， 以87%的产率得到1-[(1R,2S)-2-hydroxy-1,7,7-trimethylbicyclo[2.2.1]hept-2-yl]propan-2-one
  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
• 作为产物：
  描述：

  白樟油 、 甲基烯丙基溴化镁 在 盐酸 、 水 、 氯化铵 作用下， 以 乙醚 为溶剂， 反应 5.0h， 以87%的产率得到(1R,2S)-2-exo-hydroxy-2-endo-(2-methylallyl)-1,7,7-trimethylbicyclo<2.2.1>heptane
  参考文献：
  名称：

  Stereoselective synthesis of spirocyclic cyclopentapyrans by the Pauson–Khand reaction on camphor tethered enynes

  摘要：

  An intramolecular Pauson-Khand reaction of camphor tethered enynes derived from homoallyl, homomethallyl and homopropargyl alcohols is described. Homoallyl, homomethallyl, and homopropargyl moieties are easily constructed on the camphor carbonyl group with excellent diastereoselectivity due to endo-face selectivity, and with known stereochemistry. Each enantiomerically pure enyne affords the conformationally most stable diastereomeric spirocyclic cyclopenta[c]pyran ring system. (C) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2008.11.020

文献信息

• Synthesis and absolute configuration of new chiral epoxyalcohols by stereoselective epoxidation of allylic and homoallylic alcohols with a (1R)-(+)-camphor skeleton
  作者：Vladimir Dimitrov、Irena Philipova、Svetlana Simova

  DOI：10.1016/0957-4166(96)00168-1

  日期：1996.5

  100% diastereoselectively to 10. The epoxyalcohol 10 underwent a stereoselective intramolecular cyclisation during the epoxydation with rearrangement of the camphor skeleton to the oxatricyclo derivative 11. The absolute configurations of the new chiral compounds were determined by NMR methods.

  VO（acac）2 /叔丁基氢过氧化物体系将手性非外消旋醇1-5立体选择性环氧化。由醇1-4生成的环氧醇6-9可以高收率合成，所得非对映异构体经色谱分离为纯净形式。均丙醇5将100％非对映选择性地环氧化为10。环氧醇10在环氧化过程中经历了立体选择性的分子内环化作用，其中樟脑骨架重排为氧三环衍生物11。通过NMR方法确定了新的手性化合物的绝对构型。
• Highly effective and practical stereoselective synthesis of new homoallylic alcohols with (+)-camphor and (−)-fenchone skeleton
  作者：Vladimir Dimitrov、Svetlana Simova、Kalina Kostova

  DOI：10.1016/0040-4020(95)01005-x

  日期：1996.1

  The new chiral nonracemic homoallylic exo-alcohols 6, 7, 10 with (1R)-(+)-camphor (1) and endo-alcohols 8, 9, 11 with (1R)-(−)-fenchone (2) skeleton were synthesized in high yields by the stereoselective addition of allyl and substituted allylic Grignard reagents 3–5 to 1 and 2, respectively. The addition of the 2-butenyl (crotyl) reagent 5 occurred with high selectivity leading exclusively to α-methylallyl

  的新的手性非外消旋高烯丙基外型-醇6，7，10与（1 - [R ） - （+） -樟脑（1）和内切-醇8，9，11与（1 - [R ）- （ - ） -葑酮（2）分别通过立体选择性地添加烯丙基和取代的烯丙基格氏试剂3-5至1和2可以高产率合成骨架。2-丁烯基（巴豆基）试剂5的添加以高选择性发生，仅导致α-甲基烯丙基醇10与酮1和（Ž）-2-丁烯基醇11与酮2。均一醇6-11的绝对构型是通过NMR方法确定的。
• Synthesis of new optically active 1,3-diols with camphor and fenchone skeleton
  作者：Vladimir Dimitrov、Kalina Kostova、Manfred Hesse

  DOI：10.1016/s0957-4166(00)86259-x

  日期：1994.10

  The new optically active 1,3-diols 5–8 with (1R)-(+)-camphor and (1R)-(−)-fenchone skeleton were synthesized in high yields from the homoallylic alcohols 1–4 using a very effective ozonolysis followed by reduction. The absolute configuration of (1R, 2S, 12R)-6a was determined by a single crystal X-ray study.

  新的光学活性的1,3-二醇5-8用（1 - [R ）- （+） -樟脑和（1 - [R ）- （ - ） -葑酮骨架中从高烯丙基醇高收率合成1-4使用非常有效的臭氧分解，然后还原。通过单晶X射线研究确定（1 R，2 S，12 R）-6a的绝对构型。