1-(((trifluoromethyl)sulfonyl)oxy)-3(R)-methyl-6(S)-isopropylcyclohexene | 125950-36-9

• 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: 1-(((trifluoromethyl)sulfonyl)oxy)-3(R)-methyl-6(S)-isopropylcyclohexene
• 英文别名: 3(R)-methyl-6(S)-isopropylcyclohex-1-en-1-yl trifluoromethanesulfonate；(3R,6S)-6-isopropyl-3-methylcyclohex-1-en-1-yl trifluoromethanesulfonate；6-isopropyl-3-methylcyclohex-1-en-1-yl trifluoromethanesulfonate；(6S)-isopropyl-(3R)-methylcyclohex-1-enyl trifluoromethanesulfonate；(3R,6S)-6-isopropyl-3-methyl-1-cyclohexen-1-yl trifluoromethanesulfonate；[(3R,6S)-3-methyl-6-propan-2-ylcyclohexen-1-yl] trifluoromethanesulfonate
• CAS: 125950-36-9
• 化学式: C₁₁H₁₇F₃O₃S
• 分子量: 286.315
• InChiKey: NTXOGOFXRAURHA-BDAKNGLRSA-N

物化性质

• 沸点：
  294.4±40.0 °C(Predicted)
• 密度：
  1.25±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  51.8
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1-(((trifluoromethyl)sulfonyl)oxy)-3(R)-methyl-6(S)-isopropylcyclohexene 在 bis(1,5-cyclooctadiene)nickel (0) 、 lithium chloride 作用下， 以 四氢呋喃 、 N,N-二甲基乙酰胺 为溶剂， 反应 16.0h， 以94%的产率得到(3R,6S)-1-chloro-6-isopropyl-3-methylcyclohex-1-ene
  参考文献：
  名称：

  镍催化烯醇三氟甲磺酸酯转化为烯基卤化物。

  摘要：

  开发了镍催化的烯醇三氟甲磺酸酯卤化反应，能够在温和的反应条件下合成多种烯基碘化物、溴化物和氯化物。该反应使用廉价、实验室稳定的 Ni(OAc)2·4 H2 O 作为预催化剂，并在亚化学计量的 Zn 和 1,5-环辛二烯或 4-(N,N-二甲基氨基) 存在下在室温下进行吡啶。

  DOI：

  10.1002/anie.201906815
• 作为产物：
  描述：

  (+)-薄荷酮 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 生成 1-(((trifluoromethyl)sulfonyl)oxy)-3(R)-methyl-6(S)-isopropylcyclohexene
  参考文献：
  名称：

  Stereocontrolled Synthesis of 6-s-cis- and 6-s-trans-Locked 9Z-Retinoids by Hydroxyl-Accelerated Stille Coupling of (Z)-Tri-n-Butylstannylbut-2-en-1-ol and Bicyclic Dienyl Triflates

  摘要：

  Analogues of 9-cis-retinoic acid with locked 6-s-cis and 6-s-trans conformations have been stereoselectively synthesized using a Stille coupling reaction between bicyclic dienyl triflates (5 and 6, respectively) and (Z)-tributylstannylbut-2-en-1-ol (7) to stablish the Z geometry of the polyenic side chain. The mild conditions (25 degrees C, 30 min) of this coupling stand in contrast to the reluctance of the isomeric (E)-tributylstannylbut-2-en-1-ol (18) to react with triflates 5/6. The significant rate differences experimentally observed in Stille reactions between isomeric (Z)- and (E)-tri-n-butylstannylalkenols in favor of the former isomer, even with highly hindered alkenyl triflates, is ascribed to internal coordination of palladium to the heteroatom in the presumably rate-limiting transmetalation step. Dienals and trienals with an E geometry, which are not efficiently available by direct coupling of the corresponding triflates and E-stannanes, can in turn be obtained by isomerization of their Z-isomers.

  DOI：

  10.1021/jo9917588

文献信息

• Electrochemical Deoxygenative Thiolation of Preactivated Alcohols and Ketones
  作者：Feng Zhang、Yang Wang、Yi Wang、Yi Pan

  DOI：10.1021/acs.orglett.1c02738

  日期：2021.10.1

  This work describes an electrochemically promoted nickel-catalyzed deoxygenative thiolation of alcohols and ketones under mild conditions. Excellent substrate tolerance and good chemical yields can be achieved by graphene/nickel foam electrodes in an undivided cell. Further study to gain mechanistic insight into this electrochemical cross-coupling has been carried out.

  这项工作描述了一种电化学促进的镍催化的醇和酮在温和条件下的脱氧硫醇化反应。石墨烯/泡沫镍电极可以在未分割的电池中实现出色的基材耐受性和良好的化学产率。已经进行了进一步研究以获得对这种电化学交叉耦合的机械洞察力。
• Replacement of the hydrophobic part of 9-cis-retinoic acid with cyclic terpenoid moiety results in RXR-selective agonistic activity
  作者：Takashi Okitsu、Kana Sato、Kinya Iwatsuka、Natsumi Sawada、Kimie Nakagawa、Toshio Okano、Shoya Yamada、Hiroki Kakuta、Akimori Wada

  DOI：10.1016/j.bmc.2011.03.033

  日期：2011.5

  Retinoid X receptor (RXR) agonists are interesting candidates for the treatment of metabolic syndrome. 9-Cis-retinoic acid (9cRA: 1) is a natural RXR agonist, that also works as a retinoic acid receptor (RAR) agonist. This fact prompted us to study the structure–activity relationship (SAR) of RXR agonists derived from 1. Though 3 and 4, in which the cyclohexene part of 1 is replaced with bulkier hydrophobic

  维甲酸X受体（RXR）激动剂是治疗代谢综合征的有趣候选药物。9-顺式视黄酸（9cRA：1）是天然的RXR激动剂，其还用作视黄酸受体（RAR）激动剂。这一事实促使我们研究源自1的RXR激动剂的构效关系（SAR）。虽然是3和4，其中1的环己烯部分被更大的疏水部分取代，表现出RXR选择性激动活性，一些含有其他环结构的类似物表现出RAR激动活性。因此，我们对确定RXR选择性激动活性需要什么样的环骨架感兴趣。在这项研究中，我们系统地制备了5和6，其中1的环己烯环被各种环状萜类部分取代，并评估了它们的RXR和RAR激动活性。我们先前报道的CsF促进的Stille偶联反应被用作5和6的全面合成的关键步骤。转录分析结果表明，化合物5b – f，具有薄荷烷骨架，表现出RXR选择性激动活性。这些结果应有助于基于1的结构设计出色的RXR选择性激动剂。
• Caesium fluoride-promoted Stille coupling reaction: an efficient synthesis of 9Z-retinoic acid and its analogues using a practical building block
  作者：Takashi Okitsu、Kinya Iwatsuka、Akimori Wada

  DOI：10.1039/b813760a

  日期：——

  A highly efficient and rapid total synthesis of 9Z-retinoic acid was accomplished by caesium fluoride-promoted Stille coupling reaction; using a common building block, 9Z-retinoic acid analogues were also prepared by the same method without isomerisation of the Z-double bond.

  通过氟化铯促进的Stille偶联反应，成功实现了9Z-维甲酸的高效快速全合成；利用常见的构建模块，通过同一方法，无需Z双键的异构化，也制备了9Z-维甲酸类似物。
• Ni(^4-tBustb)₃: A Robust 16-Electron Ni(0) Olefin Complex for Catalysis
  作者：Lukas Nattmann、Josep Cornella

  DOI：10.1021/acs.organomet.0c00485

  日期：2020.9.28

  Sixteen-electron Ni(0) complexes bearing trans-stilbene derivative ligands have been shown to display a high degree of stability toward oxidation in the solid state. A structural analysis of a unique family of tris Ni(0) stilbene complexes revealed a remarkable effect of the steric hindrance of the substituents at the para position of the stilbene unit to temperature, oxidation, and degradation in solution

  带有反式二苯乙烯衍生物配体的十六电子Ni（0）配合物已显示出对固态氧化具有很高的稳定性。三的Ni（0）配合物茋的独特家族的结构分析揭示了取代基的空间位阻在一个显着的效果对二苯乙烯单元的温度，氧化和退化在溶液中的位置。根据这些分析，Ni（4-tBu stb）3作为长期的空气，实验台出现。和温度稳定的Ni（0）配合物。重要的是，Ni（4-tBu stb）3作为Ni（0）源具有更快的动力学曲线和更广阔的范围，因此优于先前描述的Ni（4-CF3）stb）3在各种相关的Ni催化转化中。
• Dual Gold‐Catalyzed Formal Tetradehydro‐Diels–Alder Reactions for the Synthesis of Carbazoles and Indolines
  作者：Hong‐Fa Wang、Shi‐Yue Wang、Tian‐Zhu Qin、Weiwei Zi

  DOI：10.1002/chem.201804529

  日期：2018.12.5

  dual gold‐catalyzed tetradehydro‐Diels–Alder reaction for the synthesis of nitrogen‐containing aromatic heterocycles. Under the catalytic system (IPrAuNTf2/DIPEA), indolines and carbazoles as well as other N‐containing aromatic heterocycles were prepared in high yields with good functional group tolerance. Unlike the traditional thermal tetradehydro‐Diels–Alder reactions, diluted reaction concentration

  这项工作报告了双重金催化的四氢-狄尔斯-阿尔德反应，用于合成含氮芳族杂环。在催化体系（IPrAuNTf 2 / DIPEA）下，以高收率和良好的官能团耐受性制备了二氢吲哚和咔唑以及其他含N的芳族杂环。与传统的热四氢-狄尔斯-阿尔德反应不同，该方案不需要稀释的反应浓度和自由基抑制剂。实验数据支持了涉及亚乙烯基金物质的机制，该机制经历了6π电环化，然后发生1,2-氢转移。