(Z)-1-<2-(1-bromovinyl)>cyclohexene

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 乙烯基卤化物
• 英文名称: (Z)-1-<2-(1-bromovinyl)>cyclohexene
• 英文别名: 1-(Z)-2-bromoethenylcyclohexene；(Z)-1-(2-bromovinyl)cyclohex-1-ene；1-[(Z)-2-bromoethenyl]cyclohexene
• 化学式: C₈H₁₁Br
• 分子量: 187.079
• InChiKey: VMRCGRRGFUYOFC-SREVYHEPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  1,1-dibromo-2-cyclohexenylethene 在 四(三苯基膦)钯 、 三正丁基氢锡 作用下， 反应 0.5h， 以66%的产率得到(Z)-1-<2-(1-bromovinyl)>cyclohexene
  参考文献：
  名称：

  Stereoselective Hydrogenolysis of 1,1-Dibromo-1-alkenes and Stereospecific Synthesis of Conjugated (Z)-Alkenyl Compounds

  摘要：

  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.

  DOI：

  10.1021/jo9812781

文献信息

• Zirconium-Catalyzed Synthesis of Alkenylaminoboranes: From a Reliable Preparation of Alkenylboronates to a Direct Stereodivergent Access to Alkenyl Bromides
  作者：Mélodie Birepinte、Virginie Liautard、Laurent Chabaud、Mathieu Pucheault

  DOI：10.1021/acs.orglett.0c00908

  日期：2020.4.3

  A simple procedure has been optimized for the preparation of alkenylaminoborane from alkynes using diisopropylaminoborane and HZrCp2Cl. Coupled with a magnesium-catalyzed dehydrogenation, it allowed for the use of air- and moisture-stable diisopropylamine. This synthesis has been extended to a one-pot sequence leading directly to bromoalkenes with controlled stereochemistry. As such, it provides an

  已优化了使用二异丙基氨基硼烷和HZrCp 2 Cl从炔烃制备烯基氨基硼烷的简单方法。结合镁催化的脱氢作用，可以使用空气和水分稳定的二异丙胺。该合成已扩展至一锅法序列，可在受控的立体化学条件下直接生成溴代烯烃。这样，它提供了一种容易，可扩展，廉价的方法来从商业上可获得的炔烃中获取烯基硼酸酯和（E）-和（Z）-溴代烯烃。
• METHOD FOR PREPARING ALKENYL AMINOBORANES AND THEIR DERIVATIVES, AND USES THEREOF
  申请人：UNIVERSITE DE BORDEAUX

  公开号：US20220396591A1

  公开（公告）日：2022-12-15

  Disclosed is a method for preparing alkenyl aminoboranes and their derivatives, and uses thereof. The method for preparing alkenyl aminoboranes includes contacting, preferably in a single synthesis step, a terminal alkyne, an aminoborane and a catalyst chosen from Schwartz's reagent (Cp2ZrHCl), dicyclohexylborane (HBCy), diisopinocamphenylborane (HBipc2) and 9-Borabicyclo(3.3.1)nonane (9-BBN).

  本发明公开了一种制备烯基氨基硼烷及其衍生物以及其用途的方法。制备烯基氨基硼烷的方法包括在单一合成步骤中接触末端炔烃、氨基硼烷和从Schwartz试剂（Cp2ZrHCl）、二环己基硼烷（HBCy）、二异螺环基硼烷（HBipc2）和9-硼杂双环[3.3.1]庚烷（9-BBN）中选择的催化剂。
• A new entry of highly nucleophilic CHBr3–TiCl4–Mg system for the stereoselective synthesis of 1-alkenyl bromides
  作者：Yeshwant Ramchandra Bhorge、Su-Haur Chang、Cheng-Ta Chang、Tu-Hsin Yan

  DOI：10.1016/j.tet.2012.03.123

  日期：2012.6

  This TiCl4-Mg promoted coupling of CHBr3 with various aldehydes and ketones, especially in sterically hindered or enolizable ketones, provides a simple, practical, and stereoselective carbonyl-bromomethylenation leading primarily to (E)-vinyl bromides. Crown Copyright (C) 2012 Published by Elsevier Ltd. All rights reserved.