ethyl 2,2-dimethylhex-5-enoate | 73062-97-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: ethyl 2,2-dimethylhex-5-enoate
• 英文别名: ethyl 2,2-dimethyl-5-hexenoate；2,2-dimethyl-hex-5-enoic acid ethyl ester；2,2-Dimethyl-5-hexenoic acid ethyl ester
• CAS: 73062-97-2
• 化学式: C₁₀H₁₈O₂
• 分子量: 170.252
• InChiKey: KPZKSADDJZMHQF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  12
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  ethyl 2,2-dimethylhex-5-enoate 在 lithium aluminium tetrahydride 、 五氯化磷 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 二氯甲烷 为溶剂， 反应 74.0h， 生成 1,1,3-三甲基环戊烷
  参考文献：
  名称：

  Mechanism of Reaction of Geminal Dihalides with Lithium Aluminum Hydride. Evidence for Single Electron Transfer as the Major Reaction Pathway

  摘要：

  The reactions of a sterically hindered geminal dichloride 4a and the corresponding diiodide 4b with LiAlH4 (LAH) were found to involve an electron-transfer mechanism. Whereas the monochloro analog of 4a (8) is inert toward LAH, 4a was more reactive. Observation of radical-derived products in the reaction of 4a with LAH indicates that the presence of two chlorine atoms on the same carbon atom results in a favorable reduction potential for 4a, as compared to 8. These results show that LAH can function as a one-electron donor toward geminal dichlorides. It was found that the diiodo analog 4b is more reactive toward LAH than 4a due to the inherent favorable reduction potentials of alkyl iodides compared to chlorides. The reactivity of 4b toward LAH was also found to be greater than that of the monoiodo analog (Ib) in keeping with the more favorable reduction potential of the diiodide (4b) compared to the monoiodide (Ib). The rates of cyclization of the corresponding haloalkyl radicals generated from 4a and 4b were also determined and were found to be 7.4 x 10(5)/s for the chloroalkyl and 5.5 x 10(5)/s for the iodoalkyl radical at 25 degrees C. The formation of small amounts of the carbene-derived product, 5, in the reactions of both 4a and 4b with LAH appeared to be preceded by a radical intermediate.

  DOI：

  10.1021/jo00093a011
• 作为产物：
  描述：

  4-溴-1-丁烯 在 正丁基锂 、 二异丙胺 、 盐酸 作用下， 以 四氢呋喃 、 乙醚 、 六甲基磷酰三胺 、 水 为溶剂， 反应 5.58h， 以75%的产率得到ethyl 2,2-dimethylhex-5-enoate
  参考文献：
  名称：

  HCV NS3 protease inhibitors

  摘要：

  本发明涉及一种公式（I）的大环化合物，该化合物可用作乙型肝炎病毒（HCV）NS3蛋白酶的抑制剂，其合成以及用于治疗或预防HCV感染的用途。

  公开号：

  US20070027071A1

文献信息

• FATTY ACID COMPOUND, PREPARATION METHOD THEREFOR AND USE THEREFOR
  申请人：SHANGHAI INSTITUTE OF MATERIA MEDICA, CHINESE ACADEMY OF SCIENCES

  公开号：US20190039989A1

  公开（公告）日：2019-02-07

  The present invention relates to a class of fatty acid compounds, a preparation method thereof and use thereof. The fatty acid compounds have the structure of the formula I, which has the ability to activate APMK and inhibit the glucose output in mouse primary hepatocytes. The fatty acid compounds can be used in preparing a medicament for the treatment of obesity or diabetes.

  本发明涉及一类脂肪酸化合物，其制备方法和用途。这些脂肪酸化合物具有式I的结构，具有激活APMK并抑制小鼠原代肝细胞中葡萄糖输出的能力。这些脂肪酸化合物可用于制备治疗肥胖或糖尿病的药物。
• Preparation of Functionalized Alkylmagnesium Derivatives Using an I/Mg-Exchange
  作者：Christian B. Rauhut、Viet Anh Vu、Fraser F. Fleming、Paul Knochel

  DOI：10.1021/ol8000987

  日期：2008.3.1

  Functionalized alkylmagnesium reagents bearing an acetal, a ketal, an ester, or a pyridine ring were prepared by an I/Mg-exchange using iPr2Mg.LiCl or ClMg(CH2)5MgCl.2LiCl starting from functionalized primary alkyl iodides.

  带有乙缩醛，缩酮，酯或吡啶环的官能化烷基镁试剂是通过i / Mg交换使用iPr2Mg.LiCl或ClMg（CH2）5MgCl.2LiCl从官能化伯烷基碘开始制备的。
• Asymmetric “Clip-Cycle” Synthesis of Pyrrolidines and Spiropyrrolidines
  作者：Christopher J. Maddocks、Kristaps Ermanis、Paul A. Clarke

  DOI：10.1021/acs.orglett.0c03090

  日期：2020.10.16

  increasingly important scaffolds in drug discovery programs, is reported. Cbz-protected bis-homoallylic amines were activated by “clipping” them to thioacrylate via an alkene metathesis reaction. Enantioselective intramolecular aza-Michael cyclization onto the activated alkene, catalyzed by a chiral phosphoric acid, formed a pyrrolidine. The reaction accommodated a range of substitutions to form 2,2- and 3,3-disubstituted

  据报道，在药物发现计划中，越来越重要的2,2-和3,3-二取代的吡咯烷和螺吡咯烷的不对称“夹子循环”合成已经得到发展。Cbz保护的双均烯丙基胺是通过烯烃易位反应将其“剪切”为硫代丙烯酸酯而活化的。通过手性磷酸催化的对映选择性分子内氮杂-Michael环化到活化的烯烃上，形成吡咯烷。反应进行了一系列取代，形成了具有高对映选择性的2，2-和3，3-二取代的吡咯烷和螺吡咯烷。通过与含酮和含氧酸酯的底物进行比较，证明了硫酯活化基团的重要性。DFT研究支持将aza-Michael环化作为决定速率和立体化学的步骤，并正确预测了主要对映异构体的形成。催化不对称合成具有“ DNA结合”和抗菌特性的N-甲基吡咯烷生物碱（R）-吡啶和（R）-bgugaine是使用“夹环”方法获得的。
• Platinum-Catalyzed Intramolecular Hydrohydrazination: Evidence for Alkene Insertion into a Pt−N Bond
  作者：Jessica M. Hoover、Antonio DiPasquale、James M. Mayer、Forrest E. Michael

  DOI：10.1021/ja906563z

  日期：2010.4.14

  regioisomeric products, only the product of 5-exo cyclization at the proximal nitrogen is formed, without reaction at the distal nitrogen or 6-endo cyclization. The resting states were found to be a 2:1 Pt-amidate complex (25, for N-acetamido) of the deprotonated hydrazide and a Pt-alkyl complex of the cyclized pyrrolidinone (20 for N-phthalimido). Both complexes are catalytically competent. Catalysis using

  发现双阳离子 (bpy) Pt(II) 配合物可催化烯烃的分子内氢化。反应优化表明 DMF-d(7) 中的 Pt(bpy)Cl(2) (10 mol %) 和 AgOTf (20 mol %) 是将取代酰肼转化为五元和六元 N 的有效催化剂体系-氨基内酰胺（N-氨基 = 120 摄氏度时的 N-乙酰氨基，80 摄氏度时的 N-邻苯二甲酰亚胺，(-)OTf = 三氟甲磺酸盐）。在四种可能的区域异构产物中，仅在近端氮形成 5-外环化产物，而在远端氮或 6-内环化没有反应。发现静止状态是去质子化酰肼的 2:1 Pt-酰胺化物络合物（25，对于 N-乙酰氨基）和环化吡咯烷酮的 Pt-烷基络合物（对于 N-邻苯二甲酰亚胺，20）。两种复合物都具有催化能力。使用 25 作为预催化剂的催化显示对添加的酸 (HOTf) 或碱 (2,6-二甲基吡啶) 没有速率依赖性。现有的机理数据都与涉及 NH 活化酰肼的机制一致，然后将烯烃插入
• Towards Stapling of Helical Alleno-Acetylene Oligomers - Synthesis of an Enantiopure Bis(ethynylvinylidene)-Substituted Cyclohexadeca-1,3,9,11-tetrayne
  作者：I.-E. Sophie Müller、Bruno Bernet、Cagatay Dengiz、W. Bernd Schweizer、François Diederich

  DOI：10.1002/ejoc.201301529

  日期：2014.2

  alleno-acetylene dimer decorated with lateral olefinic side chains. Instead, enyne RCM to an enantiomerically pure dienyne occurred. We switched to the introduction of diacetylene-containing bridges and report here the 15-step synthesis of a moderately strained, enantiomerically pure cyclohexa-1,3,9,11-tetrayne with an oxidative acetylenic coupling in the key step. The chiroptical properties of the new compounds

  我们有兴趣开发桥接（“主食”）对映异构纯无环丙炔-炔低聚物的策略，以增强它们对螺旋二级结构的构象偏好，这被认为是其特殊手性光学特性的起源。我们发现，已用于肽螺旋装订的闭环复分解 (RCM) 因用侧链烯烃侧链装饰的无环丙炔-乙炔二聚体而失败。取而代之的是，烯炔 RCM 变为对映异构纯二炔。我们转而引入含丁二炔的桥，并在此报告了中等应变、对映异构纯的环己-1,3,9,11-四炔的 15 步合成，其中关键步骤是氧化乙炔偶联。讨论了新化合物的手性特性。