(E)-1-(3-methyl1-butenyl)boronic acid | 70813-75-1

• 物质功能分类: 医药中间体 - 原料药中间体
• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 硼酸衍生物
• 英文名称: (E)-1-(3-methyl1-butenyl)boronic acid
• 英文别名: 3-methylbut-1-enylboronic acid；(E)-(3-methylbut-1-en-1-yl)boronic acid；(3-methyl-but-1-en-t-yl)-boronic acid；[(1E)-3-Methylbut-1-en-1-yl]boronic acid；[(E)-3-methylbut-1-enyl]boronic acid
• CAS: 70813-75-1
• 化学式: C₅H₁₁BO₂
• 分子量: 113.952
• InChiKey: LFWFFPWFHYNDPI-ONEGZZNKSA-N

物化性质

• 沸点：
  201.3±23.0 °C(Predicted)
• 密度：
  0.933±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.21
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 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：

  (E)-1-(3-methyl1-butenyl)boronic acid 在 sodium hydroxide 、 碘 作用下， 以 乙醚 为溶剂， 生成 (E)-1-iodo-3-methylbut-1-ene
  参考文献：
  名称：

  Stereospecific synthesis of the side chain of the steroidal plant sex hormone oogoniol

  摘要：

  DOI：

  10.1021/jo01333a021
• 作为产物：
  描述：

  (E)-4,4,5,5-tetramethyl-2-(3-methylbut-1-en-1-yl)-1,3,2-dioxaborolane 在 sodium periodate 、 ammonium acetate 、 水 作用下， 以 丙酮 为溶剂， 生成 (E)-1-(3-methyl1-butenyl)boronic acid
  参考文献：
  名称：

  Preparation of α-Imino Aldehydes by [1,3]-Rearrangements of O-Alkenyl Oximes

  摘要：

  The synthesis of alpha-imino aldehydes has been achieved through the thermal [1,3]-rearrangement of O-alkenyl benzophenone oximes. A copper. mediated C-O bond coupling between benzophenone oxime and alkenyl boronic acids provides facile access to the required O-alkenyl oximes and a Horner-Wadsworth-Emmons olefination can be applied to the a-imino aldehyde products to give gamma-imino-alpha,beta-unsaturated esters. The scope of the method is described and mechanistic experiments are discussed.

  DOI：

  10.1021/ol402237w

文献信息

• A Tunable Route to Prepare α,β-Unsaturated Esters and α,β-Unsaturated-γ-Keto Esters through Copper-Catalyzed Coupling of Alkenyl Boronic Acids with Phosphorus Ylides
  作者：Hong-Yan Bi、Feng-Ping Liu、Cui Liang、Gui-Fa Su、Dong-Liang Mo

  DOI：10.1002/adsc.201701640

  日期：2018.4.3

  strategy to prepare α,β‐unsaturated esters and α,β‐unsaturated‐γ‐keto esters in good to excellent yields was developed through copper‐catalyzed oxidative coupling of phosphorus ylides with alkenyl boronic acids under mild conditions. The reaction without water afforded α,β‐unsaturated esters, ketones, and amides while α,β‐unsaturated‐γ‐keto esters, 1,4‐α,β‐unsaturated diketones and α,β‐unsaturated‐γ‐keto

  通过在温和的条件下通过铜催化的磷化磷与烯基硼酸的氧化偶联反应，开发了一种可调谐策略，以高至极好的收率制备α，β-不饱和酯和α，β-不饱和γ-酮酯。不加水的反应得到α，β-不饱和酯，酮和酰胺，而α，β-不饱和γ-酮酯，1,4-α，β-不饱和二酮和α，β-不饱和γ-酮酰胺是使用5.0当量时获得。水。高2 O 18标记实验表明，水在α，β-不饱和γ-酮酸酯的形成中起着重要作用。在机理研究的基础上，提出了α，β-不饱和酯和α，β-不饱和γ-酮酯的合理形成机理。salts盐也可以代替磷化磷化物直接用作偶联伴侣。该反应表现出广泛的底物范围，良好的官能团耐受性，良好的区域选择性和多种偶联产物。
• Asymmetric Synthesis of α-Aminoboronic Acid Derivatives by Copper-Catalyzed Enantioselective Hydroamination
  作者：Daiki Nishikawa、Koji Hirano、Masahiro Miura

  DOI：10.1021/jacs.5b09773

  日期：2015.12.23

  A copper-catalyzed regio- and enantioselective hydroamination of alkenyl dan boronates (dan =1,8-diaminonaphthyl) with hydrosilanes and hydroxylamines proceeds to deliver the chiral α-aminoboronic acids in good yields with high enantiomeric ratios. The key to success is the introduction of an umpolung, electrophilic amination strategy. The copper catalysis can provide an unprecedented catalytic asymmetric

  铜催化的烯基丹硼酸酯（dan = 1,8-二氨基萘基）与氢硅烷和羟胺的区域选择性和对映选择性加氢胺化以高对映体比以良好的产率提供手性α-氨基硼酸。成功的关键是引入 umpolung、亲电胺化策略。铜催化可以为在有机合成和药物化学领域具有巨大潜力的烷基取代手性α-氨基硼酸衍生物提供前所未有的催化不对称方法。
• Iodine(III)-Mediated Electrochemical Trifluoroethoxylactonisation: Rational Reaction Optimisation and Prediction of Mediator Activity
  作者：Robert Möckel、Emre Babaoglu、Gerhard Hilt

  DOI：10.1002/chem.201804152

  日期：2018.10.22

  A new electrochemical iodine(III)‐mediated cyclisation reaction for the synthesis of 4‐(2,2,2‐trifluoroethoxy)isochroman‐1‐ones is presented. Based on this reaction design of experiments and multivariate linear regression analysis were used to demonstrate their first application in an electrochemical reaction. The broad applicability of these reaction conditions could be shown by a range of substrates

  提出了一种新的电化学碘（III）介导的环化反应，用于合成4-（2,2,2-三氟乙氧基）异苯并二氢吡喃-1-酮。基于该反应设计的实验和多元线性回归分析用于证明其在电化学反应中的首次应用。这些反应条件的广泛适用性可以通过一系列底物和广泛的相容性测试来证明。
• Stereoselective Hydrogenolysis of 1,1-Dibromo-1-alkenes and Stereospecific Synthesis of Conjugated (<i>Z</i>)-Alkenyl Compounds
  作者：Jun'ichi Uenishi、Reiko Kawahama、Osamu Yonemitsu、Jiro Tsuji

  DOI：10.1021/jo9812781

  日期：1998.11.1

  The Pd-catalyzed hydrogenolysis of 1,1-dibromoalkenes with Bu3SnH occurs at room temperature stereoselectively to give (Z)-1-bromo-1-alkenes. We sought to determine the optimal reaction conditions and illustrate the scope of this method with 32 dibromoalkenes including alkenyl- and alkynyl-conjugated 1,l-dibromo-l-alkenes 7a-h and 2,2-disubstituted I,1-dibromo-1-alkenes 9a-f. Triphenylphosphine was the best ligand for the Pd-catalyzed hydrogenolysis. A wide range of solvents can be used for this reaction excluding EtOH, AcOH, and CHCl3. However, the reaction proceeds even in these solvents with the addition of a cosolvent or radical scavenger. The reaction of 1,1-diiodo-1-alkene (3) gave a mixture of (Z)-1-iodo-1-alkene (4), (Z)-1-tributylstannyl-1-alkene (5), and a terminal alkene 6, while that of 1,1-dichloroalkene did not occur. This selectivity can be explained by the stereoselective insertion of Pd(0) to a trans bromine-alkenyl carbon bond, successive transmetalation with Bu3SnH, and reductive elimination. The Suzuki and Sonogashira couplings of the resulting (Z)-1-bromo-1-alkenes with alkenyl(dialkoxy)borane and terminal alkyne occurred to give conjugated polyenes and enynes stereospecifically. The Pd-catalyzed hydrogenolysis of 1,l-dibromo-l-alkene and successive cross-coupling can be carried out either in a stepwise manner or in one-pot under the same Pd catalysis. These two processes should be useful for the synthesis of geometrically pure polyene and enyne with a Z-alkenyl unit.