((4-bromophenyl)buta-1,3-diyn-1-yl)trimethylsilane | 1408003-66-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: ((4-bromophenyl)buta-1,3-diyn-1-yl)trimethylsilane
• 英文别名: 4-(4-Bromophenyl)buta-1,3-diynyl-trimethylsilane
• CAS: 1408003-66-6
• 化学式: C₁₃H₁₃BrSi
• 分子量: 277.236
• InChiKey: RLIAGVOKCVZANN-UHFFFAOYSA-N

物化性质

• 沸点：
  299.1±42.0 °C(Predicted)
• 密度：
  1.25±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.68
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  ((4-bromophenyl)buta-1,3-diyn-1-yl)trimethylsilane 在 甲醇 、 铜 、 C.I.酸性橙108 、 cesium fluoride 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 10.0h， 生成 1-bromo-4-(6,6,6-trifluorohexa-1,3-diyn-1-yl)benzene
  参考文献：
  名称：

  1,1-二氯-2,2,2-三氟乙烷的三氟乙基化不对称1,3-二炔的合成

  摘要：

  使用乙醇胺作为配体的末端1,3-二炔与1,1-二氯-2,2,2-三氟乙烷（CF 3 CHCl 2）的铜介导反应以中等至良好的产率得到三氟乙基化的不对称1,3-二炔。该反应在温和的条件下进行，并且易于操作。具有较弱的吸电子基团或供电子基团的芳基，以及在1,3-二炔末端的烷基取代基是可容忍的。用该方法合成了三氟乙基化的共轭三炔。成功地实现了三氟乙基化的不对称1,3-二炔的进一步转化以提供三氟乙基取代的1,2,3-三唑和异恶唑作为应用实例。

  DOI：

  10.1016/j.tetlet.2016.11.015
• 作为产物：
  描述：

  (4-溴苯基)乙炔 、 三甲基乙炔基硅 在 四甲基乙二胺 、 氧气 、 copper(l) chloride 作用下， 以 丙酮 为溶剂， 生成 ((4-bromophenyl)buta-1,3-diyn-1-yl)trimethylsilane
  参考文献：
  名称：

  配体控制的区域发散性镍催化的甲硅烷基取代的1,3-二炔的氢氰化

  摘要：

  报道了1-芳基-4-甲硅烷基-1，3-二炔的区域发散性镍催化的氢氰化。当使用适当的双膦和膦-亚磷酸酯配体时，相同的原料可以高产率和高区域选择性转化为两种不同的烯丙基腈。DFT计算揭示了不同配体的结构特征带来了不同的炔烃插入模式，进而导致不同的区域选择性。此外，已经通过数个下游转化证明了含氰基的1，3-烯炔的合成值。

  DOI：

  10.1021/acs.orglett.1c01262

文献信息

• Cobalt-Catalyzed Cross-Benzannulation of Conjugated Enynes and Diynes
  作者：Philipp Röse、Carmen Carlota Magraner Garcia、Florian Pünner、Klaus Harms、Gerhard Hilt

  DOI：10.1021/acs.joc.5b01198

  日期：2015.7.17

  The [4 + 2] cross-benzannulation of conjugated enynes and diynes under cobalt-catalysis led to 1,2,3-trisubstituted benzene derivatives in good yields. The reaction proceeds smoothly in absolute regiospecific control when symmetrical diynes are applied. Moreover, the use of unsymmetrical diynes was investigated, resulting in the formation of the unprecedented regioisomers as major products, which is

  共轭烯和二炔在钴催化下的[4 + 2]交叉苯甲酸酯化反应可得到1,2,3-三取代苯衍生物，收率很高。当应用对称二炔时，反应在绝对区域特异性控制下顺利进行。此外，研究了不对称二炔的使用，导致形成了前所未有的区域异构体作为主要产物，这与钯催化的苯环化反应获得的结果相反。同样，可以将4-溴苯基取代的起始原料成功地应用于钴催化的过程中，这在钯催化的对应物中可能是有问题的。
• Cobalt-Catalyzed Regio- and Stereoselective Hydrosilylation of 1,3-Diynes To Access Silyl-Functionalized 1,3-Enynes
  作者：Hui Leng Sang、Yongyi Hu、Shaozhong Ge

  DOI：10.1021/acs.orglett.9b01836

  日期：2019.7.5

  A regio- and stereoselective hydrosilylation of 1,3-diynes has been developed relying on catalysts generated from bench-stable Co(acac)2 and dppp ligand. A variety of symmetrical and unsymmetrical 1,3-diynes undergo this transformation, yielding the corresponding silyl-functionalized 1,3-enynes in high yields with excellent regioselectivity. Gram-scale reactions and further transformations of the silyl-containing

  1，3-二炔的区域和立体选择性氢化硅烷化已经开发出来，它依赖于稳定的Co（acac）2和dppp配体产生的催化剂。各种对称和不对称的1,3-二炔都经历了这种转变，以高收率和良好的区域选择性产生了相应的甲硅烷基官能化的1,3-烯炔。含甲硅烷基的1,3-烯炔产物的克级反应和进一步转化突出了这种1,3-二炔共催化氢化硅烷化反应的合成效用。
• Unsymmetrical Coupling of 1-Chloroalkynes and Terminal Alkynes under ­Experimental Sonogashira Conditions
  作者：Mogens Nielsen、Mikkel Christensen、Morten Rimmen

  DOI：10.1055/s-0033-1339891

  日期：——

  The coupling of a 1-chloroalkyne and a terminal alkyne to furnish a 1,3-butadiyne under experimental Sonogashira conditions is investigated. Through competition experiments, it is found that 1-chloroalkynes provide cross-coupling products as efficiently (or slightly better) in comparison with iodobenzenes, and almost as effectively as vinyl bromides. Yet, in regard to the degree of conversion into various products, chloroalkynes are the most reactive of all the substrates examined under the explored conditions. Optimized conditions for this cross-coupling reaction are presented.
• Phenoxide-mediated Sonogashira coupling of trimethylsilylalkynes and aryliodides: practical synthesis of phenolic-hydroxy-substituted diarylethynes and 1,4-diarylbutadiynes
  作者：Masayuki Shigeta、Junji Watanabe、Gen-ichi Konishi

  DOI：10.1016/j.tetlet.2013.01.091

  日期：2013.3

  We successfully synthesized phenolic-hydroxy-substituted diarylethynes and 1,4-diarylbutadiynes from trimethylsilylalkynes and aryliodides via silyl-group-migration-induced deprotection of alkynes and the usual Sonogashira coupling. The phenol moiety, which works as a desilylating agent, can be attached to any position in the coupling partner. This improvement for Sonogashira coupling would be highly effective, especially when the coupling partner has a phenol moiety. Additionally, the stability of the migrated silyl moiety on the ethynylation of 2-iodophenol is discussed. (C) 2013 Elsevier Ltd. All rights reserved.
• Cobalt-Catalyzed Regiodivergent Stereoselective Hydroboration of 1,3-Diynes To Access Boryl-Functionalized Enynes
  作者：Hui Leng Sang、Caizhi Wu、Guan Ge Darren Phua、Shaozhong Ge

  DOI：10.1021/acscatal.9b03139

  日期：2019.11.1

  We report a regiodivergent and stereoselective hydroboration of 1,3-diynes with pinacolborane (HBpin) in the presence of cobalt catalysts generated in situ from bench-stable Co(acac)(2) and bisphosphine ligands. These cobalt catalysts were activated by the reactions with HBpin. A range of unsymmetrical and symmetrical 1,3-diynes reacted smoothly with HBpin in the presence of Co(acac)(2)/xantphos to selectively afford enynylboronate products with boron addition to the internal carbon of the 1,3-diyne unit. However, these 1,3-diynes reacted in the presence of Co(acac)(2)/dppf to form enynylboronate products with boron addition to the external carbon of the 1,3-diyne unit. These hydroboration reactions show good functional group compatibility and can be readily scaled up to gram-scales without using a drybox. Deuterium-labeling experiments suggest a cis-addition of HBpin to the less-hindered triple bond of 1,3-diynes. Furthermore, the comparison of the regioselectivity between cobalt-catalyzed hydrosilylation and hydroboration reactions of the same 1,3-diyne substrate suggests that Co(acac)(2)/xantphos-catalyzed regioselective 1,3-diyne hydroboration proceeds through a cobalt-hydride intermediate while Co(acac)(2)/dppf-catalyzed 1,3-diyne hydroboration proceed through a cobalt boryl intermediate.