trans-2-butylcyclopropylboronic acid | 284493-44-3

• 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-2-butylcyclopropylboronic acid
• 英文别名: 2-butylcyclopropylboronic acid；trans-2-n-butylcyclopropylboronic acid；(±)-(E)-(2-butylcyclopropyl)boronic acid；[(1R,2R)-2-butylcyclopropyl]boronic acid
• CAS: 284493-44-3
• 化学式: C₇H₁₅BO₂
• 分子量: 142.006
• InChiKey: JGKUHIAOLUTHAW-RNFRBKRXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.04
• 重原子数：
  10
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 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-2-butylcyclopropylboronic acid 在 双氧水 、 potassium hydrogencarbonate 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 2.0h， 以94%的产率得到(1R,2R)-(-)-2-butyl-1-cyclopropanol
  参考文献：
  名称：

  通过酰基氯与环丙基硼酸的铃木型偶联，新颖的立体控制合成1,2-反式环丙基酮。

  摘要：

  [反应：见正文]通过以Ag（2）O和K（2）CO（3）为基础，实现了环丙基硼酸与酰基氯的钯催化交叉偶联反应。通过相应的手性环丙基硼酸的反应，也获得了高度对映体富集的环丙基酮（ee> 90％）。

  DOI：

  10.1021/ol000013h
• 作为产物：
  描述：

  二碘甲烷 、 反式-1-己烯-1-基硼酸 在 锌 作用下， 以 2-甲基四氢呋喃 为溶剂， 以38 %的产率得到trans-2-butylcyclopropylboronic acid
  参考文献：
  名称：

  Mechanochemical Simmons–Smith cyclopropanationviaball-milling-enabled activation of zinc(0)

  摘要：

  本文介绍了通过球磨西蒙斯-史密斯反应无溶剂合成环丙烷的方法。

  DOI：

  10.1039/d3gc00649b

文献信息

• A practical approach to stereodefined cyclopropyl-substituted heteroarenes using a Suzuki-type reaction
  作者：Min-Liang Yao、Min-Zhi Deng

  DOI：10.1039/b001051k

  日期：——

  In the presence of Pd(PPh3)4, NaBr and KF·2H2O the cross-coupling reaction of heteroaryl triflates with trans-cyclopropylboronic acids proceeds readily to give pure trans-cyclopropyl heteroarenes in moderate to good yields. The X-ray crystallography of compound 3g and 1H-NMR spectra of all products show that the configuration of the cyclopropyl group was retained during the reaction. Under the same reaction conditions, highly optically active cyclopropyl-substituted heteroarenes (up to 94% ee) were obtained by cross-coupling of heteroary/triflates with enantiomerically enriched cyclopropylboronic acids.

  在Pd(PPh3)4、NaBr和KF·2H2O的存在下，异芳基三氟甲烷磷酸酯与反式环丙基硼酸的交叉偶联反应顺利进行，得到纯净的反式环丙基异芳烃，产率为中等到优良。化合物3g的X射线晶体学分析和所有产品的1H-NMR谱图表明，环丙基的构型在反应过程中保持不变。在相同的反应条件下，通过将异芳基/三氟甲烷磷酸酯与具有光学纯度的环丙基硼酸进行交叉偶联，可以获得高光学活性的环丙基取代异芳烃（高达94% ee）。
• A Novel Stereocontrolled Synthesis of Cyclopropyl-Substituted α,β-Unsaturated Esters: Palladium Catalyzed Cross-coupling of Cyclopropylboronic Acids with Bromoacrylates
  作者：Shao-Man Zhou、Yi-Long Yan、Min-Zhi Deng

  DOI：10.1055/s-1998-863093

  日期：1998.2

  A novel method of stereocontrolled preparing some cyclopropyl substituted α,β-unsaturated esters is described, based upon the palladium catalyzed cross-coupling reaction of bromoacrylates with trans-2-alkyl(aryl)cyclopropylboronic acids. It was found that using toluene as a solvent and in the presence of K3PO4 · 3 H2O and catalytic amount of Pd(PPh3)4 the bromoacrylates could readily take part in the cross-coupling reaction with cyclopropylboronic acids at 100 °C, giving corresponding stereodefined cyclopropyl substituted α,β-unsaturated esters in good to excellent yields.

  描述了一种新颖的立体选择性制备某些环丙基取代的α,β-不饱和酯的方法，该方法基于溴丙烯酸酯与反式-2-烷基（芳基）环丙基硼酸的钯催化交叉偶联反应。研究发现，在100°C时，使用甲苯作为溶剂，并在K3PO4·3H2O和催化剂量的Pd(PPh3)4存在下，溴丙烯酸酯可以很容易地与环丙基硼酸发生交叉偶联反应，得到相应的立体定义的环丙基取代的α,β-不饱和酯，产率良好至优异。
• Palladium-Catalyzed Cross-Coupling Reaction of Cyclopropylboronic Acids with Aryl Triflates
  作者：Min-Liang Yao、Min-Zhi Deng

  DOI：10.1055/s-2000-6313

  日期：——

  In the presence of appropriate base and NaBr, the Suzuki-type reaction of aryl triflates and trans-cyclopropylboronic acids proceed readily to give pure trans-cyclopropylarenes in good to high yields. For the reaction of general aryl triflates, the base KF · 2 H2O is efficient, but in the case of aryl triflates bearing electron donating groups, KF · 2 H2O as a base makes the unexpected phenyl-aryl exchange between the phenyl of Pd(PPh3)4 and the aryl of triflate to occur. The use of K3PO4 · 3 H2O instead of KF · 2 H2O can inhibit the unexpected phenyl-aryl exchange, but the yield of the product is somewhat decreased. The coupling reaction of aryl triflates with the optically active cyclopropylboronic acids, which were easily obtained in good yield and with good to excellent ee (up to 94%) by the asymmetric cyclopropanation of alkenylboronates with optically pure TMTA auxiliary, was also investigated. During the coupling reaction, the absolute configuration of the cyclopropyl group was retained. Thus, a novel method to prepare aryl-substituted cyclopropanes, including highly optically active cyclopropanes, from phenols or arylamines was provided.

  在适当的碱和 NaBr 存在下，芳基三氟酸酯和反式环丙基硼酸的 Suzuki 型反应很容易进行，并以良好至高产率得到纯的反式环丙基烯烃。对于一般的芳基三氟酸酯反应，碱 KF - 2 H2O 是有效的，但对于带有电子捐赠基团的芳基三氟酸酯，KF - 2 H2O 作为碱会使 Pd(PPh3)4 的苯基和三氟酸酯的芳基之间发生意想不到的苯基-芳基交换。使用 K3PO4 - 3 H2O 代替 KF - 2 H2O 可以抑制意想不到的苯基-芳基交换，但生成物的产率会有所下降。通过烯基硼酸酯与光学纯 TMTA 助剂的不对称环丙烷化反应，可以轻松获得收率高、ee 值好到极好（高达 94%）的光学活性环丙基硼酸。在偶联反应过程中，环丙基的绝对构型得以保留。因此，提供了一种从苯酚或芳基胺制备芳基取代环丙烷（包括高光学活性环丙烷）的新方法。
• Facile Approach to 4-Substituted 2(5<i>H</i>)-Furanones
  作者：Min-Liang Yao、Min-Zhi Deng

  DOI：10.1021/jo000195t

  日期：2000.8.1
• Palladium-catalyzed cross-coupling of cyclopropylboronic acids with alkenyl triflates
  作者：Min-Liang Yao、Min-Zhi Deng

  DOI：10.1016/s0040-4039(00)01655-5

  日期：2000.11

  A novel method for the synthesis of stereodefined cyclopropyl-substituted alkenes, based on the Suzuki-type cross-coupling reaction between cyclopropylboronic acids and various alkenyl triflates, is described. It was found that the environment of the alkenyl triflate plays an important role in the reaction, and that the use of an appropriate base can make the reaction proceed readily to give stereodefined cyclopropyl-substituted alkenes in good to high yield. (C) 2000 Elsevier Science Ltd. All rights reserved.