(R)-(-)-5-trimethylsilyl-2-cyclohexenone | 116215-94-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (R)-(-)-5-trimethylsilyl-2-cyclohexenone
• 英文别名: (R)-(-)-5-trimethylsilylcyclohex-2-enone；(5R)-5-trimethylsilylcyclohex-2-en-1-one
• CAS: 116215-94-2
• 化学式: C₉H₁₆OSi
• 分子量: 168.311
• InChiKey: XURQBSWHQFVSPZ-SECBINFHSA-N

物化性质

• 沸点：
  219.5±40.0 °C(Predicted)
• 密度：
  0.90±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.61
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (R)-(-)-5-trimethylsilyl-2-cyclohexenone 在 4-甲基苯磺酸吡啶 、 四氯化锡 作用下， 以 二氯甲烷 为溶剂， 反应 0.17h， 生成 (-)-3-(Ethoxycarbonylmethyl)-5-(trimethylsilyl)cyclohexanone ethyleneacetal
  参考文献：
  名称：

  Asaoka, Morio; Sonoda, Syuzo; Takei, Hisashi, Chemistry Letters, 1989, p. 1847 - 1848

  摘要：

  DOI：
• 作为产物：
  描述：

  (3S,5S)-3-(4'-methylbenzenethio)-5-(trimethylsilyl)cyclohexanone 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以100%的产率得到(R)-(-)-5-trimethylsilyl-2-cyclohexenone
  参考文献：
  名称：

  Enantioselective synthesis of the four isomers of the biologically active metabolite of the 2-arylpropanoic acid NSAID, ximoprofen, and assessment of their inhibitory activity on human platelet cyclo-oxygenase in vitro

  摘要：

  The four stereoisomers of the parent keto acid of the oximino drug ximoprofen have been prepared in high enantiomeric purity. The stereochemistry in the propionic acid chain was established by the combination of Sharpless epoxidation followed by stereoselective hydrogenolysis of the benzylic carbon-oxygen bond with inversion of configuration. The stereochemistry of the centre in the cyclohexanone ring was controlled by the stereoselective conjugate addition of the arylpropanoic acid moiety to the enantiomers of 5-(trimethylsilyl)-2-cyclohexenone with subsequent removal of the trimethylsilyl group. The pharmacological activity of each of the four isomers of the keto acid parent of ximoprofen were assessed by their in vitro inhibition of human platelet cyclo-oxygenase. As expected, the (S) configuration of the propionic acid chain was essential for activity but it was also found that the stereochemistry in the cyclohexanone moiety was important. Attempts to separate the (E) and (Z) isomers of the oxime derivative from one of the stereoisomers were unsuccessful.

  DOI：

  10.1016/0957-4166(95)00443-2

文献信息

• POLYCYCLIC CARBOGENIC MOLECULES AND USES THEREOF AS ANTI-CANCER AGENTS
  申请人：Northwestern University

  公开号：US20190127306A1

  公开（公告）日：2019-05-02

  Disclosed are new polycyclic carbogenic molecules and their methods of synthesis. The new polycyclic carbogenic molecules may be utilized in anti-cancer therapies. In particular, the polycyclic carbogenic molecules may be formulated as pharmaceutical compositions that comprise the small molecules, which compositions may be administered in methods of treating and/or preventing cell proliferative diseases and disorders such as cancer. The new polycyclic carbogenic molecules may be prepared from vinyl- or allyl-substituted cyclohexenone precursors via preparation of a silyl bis-enol ether intermediate.

  揭示了新的多环碳基分子及其合成方法。这些新的多环碳基分子可以用于抗癌疗法。特别是，这些多环碳基分子可以制成包含小分子的药物组合物，这些组合物可以在治疗和/或预防细胞增殖性疾病和癌症等疾病的方法中使用。这些新的多环碳基分子可以通过从乙烯或烯丙基取代的环己酮前体制备硅烷双烯醚中间体来制备。
• A Strategy for the Convergent and Stereoselective Assembly of Polycyclic Molecules
  作者：Emily E. Robinson、Regan J. Thomson

  DOI：10.1021/jacs.7b13234

  日期：2018.2.7

  The stereoselective oxidative coupling of cyclic ketones via silyl bis-enol ethers followed by ring-closing metathesis is shown to be a general and powerful reaction sequence for the preparation of diverse polycyclic scaffolds from simple precursors. The modular strategy successfully constructs substructures prevalent in numerous bioactive natural product families, varying in substitution and carbocyclic

  环酮通过甲硅烷基双烯醇醚的立体选择性氧化偶联，然后是闭环复分解，是从简单的前体制备多种多环支架的通用且强大的反应序列。模块化策略成功地构建了在众多生物活性天然产物家族中普遍存在的子结构，这些子结构的取代基和碳环组成各不相同。几种制备的化合物显示出对一组肿瘤细胞系具有有效的细胞毒活性。复杂的抗疟海洋二萜 (+)-7,20-二异氰基二萜的简洁且高度收敛的 17 步正式合成进一步证明了该策略的实用性。
• Highly Enantioselective Copper-Phosphoramidite Catalyzed Kinetic Resolution of Chiral 2-Cyclohexenones
  作者：Robert Naasz、Leggy A. Arnold、Adriaan J. Minnaard、Ben L. Feringa

  DOI：10.1002/1521-3773(20010302)40:5<927::aid-anie927>3.0.co;2-k

  日期：2001.3.2

  obtained enantiomerically pure by employing the chiral copper-phosphoramidite complex [Cu(OTf)2 L*] as a highly efficient catalyst for their kinetic resolution (>99 % ee at 52 % conversion, selectivity S>200). These important building blocks can be obtained on a synthetically interesting scale, as was demonstrated by the successful multigram resolution of 5-methyl-2-cyclohexenone. Tf=trifluoromethanesulfonyl

  通过使用手性铜-亚磷酰胺络合物[Cu（OTf）2 L *]作为其动力学拆分的高效催化剂，可以得到对映体纯的多种取代的2-环己酮，如（R）-1 （> 99％ ee，转化率为52％，选择性S> 200）。这些重要的结构单元可以以合成有趣的规模获得，如成功的5-甲基-2-环己烯酮的克数解析度所证明的那样。Tf ＝三氟甲磺酰基。
• Kinetic resolution of 5-substituted cycloalkenones by peptidic amidophosphane-copper-catalyzed asymmetric conjugate addition of dialkylzinc
  作者：Takahiro Soeta、Khalid Selim、Masami Kuriyama、Kiyoshi Tomioka

  DOI：10.1016/j.tet.2007.03.032

  日期：2007.7

  Asymmetric conjugate alkylation reaction of racemic 5-substituted cyclohexenones with dialkylzinc reagents was catalyzed by 2–5 mol % of dipeptidic amidophosphane-Cu(MeCN)4BF4 in toluene at 0 °C for 20 min to recover enantioenriched starting 5-substituted cyclohexenones with 88–98% ee in 28–41% yield along with trans major 3-alkylated 5-substituted cyclohexanones with 81–90% ee in 53–60% yield. Complete

  外消旋的5-取代的环己烯酮与二烷基锌试剂的不对称共轭烷基化反应是在甲苯中于0°C下通过2–5 mol％的二肽酰胺基膦-Cu（MeCN）4 BF 4催化20分钟，以回收对映体富集的起始5-取代的环己烯酮ee的产率为88-98％，ee的产率为28-41％，而反式三烷基化的5-取代的环己酮的ee产率为81-90％，产率为53-60％。由不对称催化反应的条件下与二乙基锌处理原料外消旋的5- TMS环己烯酮的完全消耗，得到的反式主要85:15混合物反式-和顺具有15％ee（对于反式）的-3-乙基-5-TMS-环己酮，其合计产率为83％，这表明环己烯酮的构象控制的烷基转移反应胜过手性催化剂控制的对面相分化。
• Trimethylsilyl group directed wagner-meerwein rearrangement of bicyclo[2.2.2]octan-2-ol derivatives
  作者：Morio Asaoka、Hisashi Takei

  DOI：10.1016/s0040-4039(01)91369-3

  日期：1987.1

  Trimethylsilyl group substituted bicyclo[2.2.2]octane derivatives were synthesized and subjected to TMS group directed Wagner-Meerwein rearrangement to give bicyclo[3.2.1]octene derivatives in high yields.

  合成三甲基甲硅烷基取代的双环[2.2.2]辛烷衍生物，并进行TMS基团定向的Wagner-Meerwein重排，以高收率得到双环[3.2.1]辛烯衍生物。