(1,4-dichloro-2-buten-2-yl)boronic acid pinacol ester | 439813-69-1

• 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: (1,4-dichloro-2-buten-2-yl)boronic acid pinacol ester
• 英文别名: 2-[(1Z)-3-chloro-1-(chloromethyl)-1-propen-1-yl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane；2-[(Z)-1,4-dichlorobut-2-en-2-yl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
• CAS: 439813-69-1
• 化学式: C₁₀H₁₇BCl₂O₂
• 分子量: 250.961
• InChiKey: IQQNNKBKRHCPPF-VMPITWQZSA-N

物化性质

• 沸点：
  263.2±50.0 °C(Predicted)
• 密度：
  1.10±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.02
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1,4-dichloro-2-buten-2-yl)boronic acid pinacol ester 在 chromium dichloride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 16.0h， 以75%的产率得到4,4,5,5-tetramethyl-2-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1-vinylcyclohex-3-en-1-yl]-1,3,2-dioxaborolane
  参考文献：
  名称：

  [4+3] versus [4+2] Mechanisms in the Dimerization of 2-Boryl-1,3-butadienes. A Theoretical and Experimental Study

  摘要：

  The thermal dimerization of 2-boryl-1,3-butadienes and the scope of this reaction to prepare sixmembered rings difficult to synthesize by other methodologies have been studied. In addition, the nature of this dimerization has been studied theoretically. It has been found that the reaction coordinate associated with the formation of the cycloadduct of lowest energy has significant [4+3] character. This behavior is caused by the favorable carbon-carbon overlap and the large values of the corresponding resonance integrals. However, beyond the transition structure, the [4+2] pathway becomes the preferred one thus leading to the exclusive formation of the [4+2] cycloadduct. Aside from this effect, donating groups at the boryl moiety favor the [4+2] mechanism.

  DOI：

  10.1021/jo026491i
• 作为产物：
  描述：

  1,4-二氯-2-丁炔 生成 (1,4-dichloro-2-buten-2-yl)boronic acid pinacol ester
  参考文献：
  名称：

  [EN] AZABICYCLO (3.1.0) HEXANE DERIVATIVES USEFUL AS MODULATORS OF DOPAMINE D3 RECEPTORS
  [FR] DERIVES AZABICYCLO (3.1.0) HEXANE UTILES COMME MODULATEURS DES RECEPTEURS D3 DE LA DOPAMINE

  摘要：

  本发明涉及公式(I)的新化合物或其药学上可接受的盐，其中G选自以下组成的一组：苯基、吡啶基、苯并噻唑基、吲哚基；p是一个从0到5的整数；R1独立地选自以下组成的一组：卤素、羟基、氰基、C1-4烷基、卤代C1-4烷基、C1-4烷氧基、卤代C1-4烷氧基、C1-4烷酰基；或对应于一个R5基团；R2是氢或C1-4烷基；R3是C1-4烷基；R4是氢，或苯基、杂环基、5-或6-成员杂芳基，或8-到11-成员双环基，其中任何一个基团可以选择地被来自以下组成的1、2、3或4个取代基所取代：卤素、氰基、C1-4烷基、卤代C1-4烷基、C1-4烷氧基、C1-4烷酰基；R5是选自以下组成的基团：异噁唑基、-CH2-N-吡咯基、1,1-二氧化-2-异噻唑啉基、噻吩基、噻唑基、吡啶基、2-吡咯烷基，这样的基团可以选择地被一个或两个取代基所取代，所述取代基选自：卤素、氰基、C1-4烷基、卤代C1-4烷基、C1-4烷氧基、C1-4烷酰基；当R1是氯且p为1时，该R1不位于与分子其余部分的连接键的邻位；当R1对应于R5时，p为1；它们的制备方法，用于这些方法的中间体，含有它们的药物组合物以及它们作为多巴胺D3受体调节剂在治疗中的用途，例如用于治疗药物依赖或作为抗精神病药物。

  公开号：

  WO2005080382A1

文献信息

• Suzuki Coupling Reactions in Heterocyclic Chemistry: Synthesis of 3-Substituted Pyrrolines and Pyrroles
  作者：Alain Hercouet、Andreas Neu、Jean-François Peyronel、Bertrand Carboni

  DOI：10.1055/s-2002-25351

  日期：——

  A simple preparation of N-substituted 3-pyrroline boromic esters from primary amines is described. The Suzuki-Miyaura coupling of these heterocycles with aryl halides proceeds in good yields. Alternatively, oxidation withDDQ or MnO 2 gives the corresponding pyrroles, which can be also engaged in subsequent palladium cross-coupling reactions.

  描述了从伯胺中简单制备 N-取代的 3-吡咯啉硼酸酯。这些杂环与芳基卤化物的 Suzuki-Miyaura 偶联以良好的产率进行。或者，用DDQ或MnO 2 氧化得到相应的吡咯，其也可参与随后的钯交叉偶联反应。
• [EN] AZABICYCLO (3.1.0) HEXANE DERIVATIVES USEFUL AS MODULATORS OF DOPAMINE D3 RECEPTORS<br/>[FR] DERIVES AZABICYCLO (3.1.0) HEXANE UTILES COMME MODULATEURS DES RECEPTEURS D3 DE LA DOPAMINE
  申请人：GLAXO GROUP LTD

  公开号：WO2005080382A1

  公开（公告）日：2005-09-01

  The present invention relates to novel compounds of formula (I) or a pharmaceutically acceptable salt thereof, wherein G is selected from a group consisting of: phenyl, pyridyl, benzothiazolyl, indazolyl; p is an integer ranging from 0 to 5; R1 is independently selected from a group consisting of: halogen, hydroxy, cyano, C1-4alkyl, haloC1-4alkyl, C1-4alkoxy, haloC1-4alkoxy, C1-4alkanoyl; or corresponds to a group R5; R2 is hydrogen or C1-4alkyl; R3 is C1-4alkyl; R4 is hydrogen, or a phenyl group, a heterocyclyl group, a 5- or 6-membered heteroaromatic group, or a 8- to 11-membered bicyclic group, any of which groups is optionally substituted by 1, 2, 3 or 4 substituents selected from the group consisting of: halogen, cyano, C1-4alkyl, haloC1-4alkyl, C1-4alkoxy, C1-4alkanoyl; R5 is a moiety selected from the group consisting of: isoxazolyl, -CH2-N-pyrrolyl, 1,1-dioxido-2-isothiazolidinyl, thienyl, thiazolyl, pyridyl, 2-pyrrolidinonyl, and such a group is optionally substituted by one or two substituents selected from: halogen, cyano, C1-4alkyl, haloC1-4alkyl, C1-4alkoxy, C1-4alkanoyl; and when R1 is chlorine and p is 1, such R1 is not present in the ortho position with respect to the linking bond to the rest of the molecule; and when R1 corresponds to R5, p is 1; processes for their preparation, intermediates used in these processes, pharmaceutical compositions containing them and their use in therapy, as modulators of dopamine D3 receptors, e.g. to treat drug dependency or as antipsychotic agents.

  本发明涉及公式(I)的新化合物或其药学上可接受的盐，其中G选自以下组成的一组：苯基、吡啶基、苯并噻唑基、吲哚基；p是一个从0到5的整数；R1独立地选自以下组成的一组：卤素、羟基、氰基、C1-4烷基、卤代C1-4烷基、C1-4烷氧基、卤代C1-4烷氧基、C1-4烷酰基；或对应于一个R5基团；R2是氢或C1-4烷基；R3是C1-4烷基；R4是氢，或苯基、杂环基、5-或6-成员杂芳基，或8-到11-成员双环基，其中任何一个基团可以选择地被来自以下组成的1、2、3或4个取代基所取代：卤素、氰基、C1-4烷基、卤代C1-4烷基、C1-4烷氧基、C1-4烷酰基；R5是选自以下组成的基团：异噁唑基、-CH2-N-吡咯基、1,1-二氧化-2-异噻唑啉基、噻吩基、噻唑基、吡啶基、2-吡咯烷基，这样的基团可以选择地被一个或两个取代基所取代，所述取代基选自：卤素、氰基、C1-4烷基、卤代C1-4烷基、C1-4烷氧基、C1-4烷酰基；当R1是氯且p为1时，该R1不位于与分子其余部分的连接键的邻位；当R1对应于R5时，p为1；它们的制备方法，用于这些方法的中间体，含有它们的药物组合物以及它们作为多巴胺D3受体调节剂在治疗中的用途，例如用于治疗药物依赖或作为抗精神病药物。
• [4+3] versus [4+2] Mechanisms in the Dimerization of 2-Boryl-1,3-butadienes. A Theoretical and Experimental Study
  作者：François Carreaux、Françoise Possémé、Bertrand Carboni、Ana Arrieta、Begoña Lecea、Fernando P. Cossío

  DOI：10.1021/jo026491i

  日期：2002.12.1

  The thermal dimerization of 2-boryl-1,3-butadienes and the scope of this reaction to prepare sixmembered rings difficult to synthesize by other methodologies have been studied. In addition, the nature of this dimerization has been studied theoretically. It has been found that the reaction coordinate associated with the formation of the cycloadduct of lowest energy has significant [4+3] character. This behavior is caused by the favorable carbon-carbon overlap and the large values of the corresponding resonance integrals. However, beyond the transition structure, the [4+2] pathway becomes the preferred one thus leading to the exclusive formation of the [4+2] cycloadduct. Aside from this effect, donating groups at the boryl moiety favor the [4+2] mechanism.