trans-6-chlorohex-1-enyl boronic acid | 852603-87-3

• 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: trans-6-chlorohex-1-enyl boronic acid
• 英文别名: 6-chlorohexenylboronic acid；[(1E)-6-Chlorohex-1-en-1-yl]boronic acid；[(E)-6-chlorohex-1-enyl]boronic acid
• CAS: 852603-87-3
• 化学式: C₆H₁₂BClO₂
• 分子量: 162.424
• InChiKey: UJEYCHSCROARBB-HWKANZROSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.96
• 重原子数：
  10
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  trans-6-chlorohex-1-enyl boronic acid 在 potassium hydrogen bifluoride 作用下， 以 乙醚 、 水 为溶剂， 反应 2.0h， 以80%的产率得到potassium (E)-(6-chlorohex-1-en-1-yl)trifluoroborate
  参考文献：
  名称：

  烯基三氟硼酸钾与烯基溴化物的立体选择性Suzuki-Miyaura交叉偶联反应

  摘要：

  描述了使用空气稳定的链烯基三氟硼酸钾作为偶联伴侣的立体选择性合成共轭二烯的方法。钯催化的（E）-和（Z）-烯基三氟硼酸钾与（E）-或（Z）-烯基溴化物的钯催化交叉偶联反应容易进行，产率中等至优异，得到相应的（E，E）- ，（E，Z）-，（Z，E）-或（Z，Z）共轭二烯立体定向。交叉耦合通常可使用5摩尔％的Pd（OAC）的实现2，10摩尔％的PPH 3和Cs的3当量2 CO 3在THF-H 2 O（10∶1）中。两种偶联伙伴均容许多种官能团。

  DOI：

  10.1021/jo050286w
• 作为产物：
  描述：

  (E)-2-(6-chlorohex-1-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 在 sodium periodate 、 ammonium acetate 、 水 作用下， 以 丙酮 为溶剂， 生成 trans-6-chlorohex-1-enyl 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。
• Dimeric Manganese‐Catalyzed Hydroalkenylation of Alkynes with a Versatile Silicon‐Based Directing Group
  作者：Yubo Pang、Shuai Chen、Jie Han、Chengjian Zhu、Chuan‐Gang Zhao、Jin Xie

  DOI：10.1002/anie.202306922

  日期：2023.8

  Herein, we present a manganese‐catalyzed, branched‐selective hydroalkenylation of terminal alkynes, under mild conditions through facile installation of a versatile silanol as a removable directing group. With an alkenyl boronic acid as the coupling partner, this reaction produces stereodefined (E,E)‐1,3‐dienes with high regio‐, chemo‐ and stereoselectivity. The protocol features mild reaction conditions such as room temperature and an air atmosphere, while maintaining excellent functional group compatibility. The resulting 1,3‐dienesilanol products serve as versatile building blocks, as the removal of the silanol group allows for the synthesis of both branched terminal 1,3‐dienes for downstream coupling reactions, as well as stereoselective construction of linear (E,E)‐1,3‐dienes and (E,E,E)‐ or (E,E,Z)‐1,3,5‐trienes. In addition, a Diels–Alder cycloaddition can smoothly and selectively deliver silicon‐containing pentasubstituted cyclohexene derivatives. Mechanistic investigations, in conjunction with DFT calculations, suggest a bimetallic synergistic activation model to account for the observed enhanced catalytic efficiency and good regioselectivity.

  摘要在此，我们介绍了一种锰催化的、支链选择性的末端炔烃加氢烯化反应，该反应是在温和的条件下，通过简便地安装一个多功能硅醇作为可移动的指导基团而实现的。以烯基硼酸为偶联剂，该反应可生成立体定向的 (E,E)-1,3-二烯，并具有高度的区域、化学和立体选择性。该方案的反应条件温和，如室温和空气环境，同时保持了极好的官能团兼容性。生成的 1,3-二烯硅烷醇产品可作为多功能构筑基块，因为去除硅烷醇基团可合成用于下游偶联反应的支链末端 1,3-二烯，以及立体选择性地构建线性 (E,E)-1,3 二烯和 (E,E,E)- 或 (E,E,Z)-1,3,5 三烯。此外，Diels-Alder 环化反应还能顺利地、选择性地生成含硅的五取代环己烯衍生物。结合 DFT 计算进行的机理研究表明，双金属协同活化模型可以解释所观察到的更高催化效率和良好的区域选择性。
• Preparation of α-Imino Aldehydes by [1,3]-Rearrangements of <i>O</i>-Alkenyl Oximes
  作者：Dimitra Kontokosta、Daniel S. Mueller、Heng-Yen Wang、Laura L. Anderson

  DOI：10.1021/ol402237w

  日期：2013.9.20

  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.
• Stereoselective Suzuki−Miyaura Cross-Coupling Reactions of Potassium Alkenyltrifluoroborates with Alkenyl Bromides
  作者：Gary A. Molander、Luciana A. Felix

  DOI：10.1021/jo050286w

  日期：2005.5.1

  The stereoselective synthesis of conjugated dienes using air-stable potassium alkenyltrifluoroborates as coupling partners is described. The palladium-catalyzed cross-coupling reaction of potassium (E)- and (Z)-alkenyltrifluoroborates with either (E)- or (Z)-alkenyl bromides proceeds readily with moderate to excellent yields to give the corresponding (E,E)-, (E,Z)-, (Z,E)-, or (Z,Z)-conjugated dienes

  描述了使用空气稳定的链烯基三氟硼酸钾作为偶联伴侣的立体选择性合成共轭二烯的方法。钯催化的（E）-和（Z）-烯基三氟硼酸钾与（E）-或（Z）-烯基溴化物的钯催化交叉偶联反应容易进行，产率中等至优异，得到相应的（E，E）- ，（E，Z）-，（Z，E）-或（Z，Z）共轭二烯立体定向。交叉耦合通常可使用5摩尔％的Pd（OAC）的实现2，10摩尔％的PPH 3和Cs的3当量2 CO 3在THF-H 2 O（10∶1）中。两种偶联伙伴均容许多种官能团。