1,1-dibromo-4-trimethylsilyl-1-buten-3-yne | 181214-42-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,1-dibromo-4-trimethylsilyl-1-buten-3-yne
• 英文别名: 4-trimethylsilyl-1,1-dibromo-1-buten-3-yne；1,1-dibromo-4-trimethylsilylbut-1-en-3-yn；1,1-dibromo-4-trimethylsilyl-but-1-ene-3-yne；4,4-Dibromobut-3-en-1-ynyl(trimethyl)silane
• CAS: 181214-42-6
• 化学式: C₇H₁₀Br₂Si
• 分子量: 282.05
• InChiKey: OJSYQPPRRFFPEM-UHFFFAOYSA-N

物化性质

• 沸点：
  193.4±33.0 °C(Predicted)
• 密度：
  1.542±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.43
• 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：

  1,1-dibromo-4-trimethylsilyl-1-buten-3-yne 在 四(三苯基膦)钯 、 三正丁基氢锡 作用下， 反应 1.0h， 以69%的产率得到(Z)-1-bromo-4-trimethylsilyl-1-buten-3-yne
  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
• 作为产物：
  描述：

  三甲硅基丙炔醇 在 4 A molecular sieve 、 三苯基膦 、 pyridinium chlorochromate 、 锌 作用下， 以 二氯甲烷 为溶剂， 反应 16.5h， 生成 1,1-dibromo-4-trimethylsilyl-1-buten-3-yne
  参考文献：
  名称：

  通过对供体和受体之间的间隔基进行系统性调节，可调节电荷转移生色团的性质。

  摘要：

  制备了一系列供体-受体生色团，其中分隔4-二甲基苯胺基（DMA）供体和C（CN）（2）受体部分的间隔基是系统地变化的。除4 b以外，所有新的推挽系统都是热稳定分子。在系列a中，DMA环直接连接至中心间隔基，而在系列b中，插入其他乙炔部分。获得了七个新的，强烈着色的目标化合物的X射线晶体结构。在系列a中，DMA环在空间上被迫离开残留pi系统的平均平面，而系列b中的整个共轭pi系统几乎是平面的。通过评估DMA环的醌型特征并通过NMR和IR光谱获得了强烈的供体-受体相互作用的支持。UV / Vis光谱特征发生了红移，对于二维扩展的生色团6a和6b，测量到了具有最低的能量跃迁和最小的光学间隙的强电荷转移带。通过循环伏安法（CV）和差分脉冲伏安法（DPV）研究了推挽分子的氧化还原行为。在系列1b，2b，4b，5b中，系统地扩大了供体和受体部分之间的间隔基，电化学间隙从1.94 V（1 b）稳定减小至1

  DOI：

  10.1002/chem.200601735

文献信息

• Highly Stereoselective Total Synthesis of Fully Hydroxy-Protected Mycolactones A and B and Their Stereoisomerization upon Deprotection
  作者：Guangwei Wang、Ning Yin、Ei-ichi Negishi

  DOI：10.1002/chem.201002627

  日期：2011.4.4

  Unprecedentedly efficient and highly (≥98 %) stereoselective syntheses of mycolactones A and B side chains relied heavily on Pd‐catalyzed alkenylation (Negishi version) and were completed in 11 longest linear steps from ethyl (S)‐3‐hydroxybutyrate in 12 % and 11 % overall yield, respectively, roughly corresponding to an average of 82 % yield per step. The synthesis of mycolactone core was realized by using Pd‐catalyzed

  真菌内酯 A 和 B 侧链的前所未有的高效和高度（≥98 %）立体选择性合成严重依赖于 Pd 催化的烯基化（Negishi 版本），并在 11 个最长的线性步骤中完成，从12% 的( S )-3-羟基丁酸乙酯和分别为 11% 的总产率，大致对应于每步平均 82% 的产率。Mycolactone核心的合成是通过使用Pd催化的烯基烯丙基偶联和与三烷基烯基铝酸盐的环氧化物开环反应作为关键步骤来实现的。首次成功合成了异构纯度≥98%的完全羟基保护的支链菌内酯A和B。然而，在脱保护后获得了出乎意料的 4:3-5:4 不可分离的支链内酯 A 和 B 混合物。
• Novel synthetic strategy towards subphthalocyanine-functionalized acetylenic scaffolds <i>via</i> various dibromo-enynes
  作者：Line Broløs、Martin Drøhse Kilde、Mogens Brøndsted Nielsen

  DOI：10.1039/d0ob00988a

  日期：——

  Boron subphthalocyanine (SubPc) is a strong chromophore with interesting applications in the field of functional materials and can be synthetically modified in both the peripheral and axial positions, allowing tuning of optical and redox properties. Herein we present novel acetylenic scaffolds where SubPc units are bridged via acetylenic moieties at the boron atoms. Specifically, we show that dibromo-functionalized

  硼亚酞菁 (SubPc) 是一种强生色团，在功能材料领域具有有趣的应用，可以在周边和轴向位置进行合成修饰，从而可以调节光学和氧化还原特性。在这里，我们提出了新的炔属支架，其中 SubPc 单元通过硼原子上的炔属部分桥接。具体来说，我们表明二溴官能化的烯炔和烯二炔单元（乙烯基二溴化物）可以使用 AlCl 3连接到一个或两个 SubPc 硼原子介导的三甲基甲硅烷基保护的炔烃的炔基化方案，这些化合物可以方便地用于进一步的 Sonogashira 或 Glaser-Hay 偶联反应。因此，获得了新的四乙炔基乙烯 (TEE) - SubPc 支架。通过循环伏安法研究了并入二聚体支架中的两个 SubPc 单元之间的通信程度。当被一个 TEE 单元桥接时，SubPc 单元的氧化顺序发生，而两个 SubPc 单元在被两个 TEE 单元隔开时表现为独立的氧化还原中心。
• Synthesis of Simple Diynals, Diynones, Their Hydrazones, and Diazo Compounds: Precursors to a Family of Dialkynyl Carbenes (R¹—C≡C—C̈—C≡C—R²)
  作者：Nathan P. Bowling、Nicola J. Burrmann、Robert J. Halter、Jonathan A. Hodges、Robert J. McMahon

  DOI：10.1021/jo101125y

  日期：2010.10.1

  A variety of substituted pentadiynols, -diynals, and -diynones have been prepared en route to precursors to dialkynyl carbenes (R-1-C C-C-C C-R-2). In light of the marginal stability associated with these simple systems, several strategies were required to assemble the carbon backbones. The requisite five-carbon skeletons were prepared using 4 + 1, 3 2, 2 + 2 + 1, and 2 + 1 + 1 + 1 coupling methodologies. The Dess Martin periodinane serves as an excellent method for the oxidation of pentadiynols to diynals and diynones, although many of the oxidized products are sufficiently reactive that they were not isolated; rather, they were generated in situ and intercepted with nucleophiles such as tosylhydrazide or trisylhydrazide. The hydrazone derivatives are generally reliable precursors to diazo compounds and carbenes, although cyclization of the hydrazone to afford a pyrazole can be a complicating factor in certain instances.
• Clean Inversion of Configuration in the Pd-Catalyzed Cross-Coupling of 2-Bromo-1,3-dienes
  作者：Xingzhong Zeng、Qian Hu、Mingxing Qian、Ei-ichi Negishi

  DOI：10.1021/ja0304392

  日期：2003.11.1

  The Pd-catalyzed cross-coupling reaction of 2-bromo-1,3-dienes derived from alkyl aldehydes, especially with Cl2Pd(DPEphos) as a catalyst, proceeds with clean stereoinversion of the Br-bearing C=C bond to produce in high yields and in high stereoselectivity (>/=97-98%) conjugated Z,E dienes of potentially high utility in the synthesis of complex natural products. The observed stereoinversion cannot be readily accommodated by the widely accepted pi-sigma-pi rearrangement mechanism for isomerization of ordinary allylpalladium derivatives.
• Stereoselective Synthesis of the Side Chains of Mycolactones A and B Featuring Stepwise Double Substitutions of 1,1-Dibromo-1-alkenes
  作者：Ning Yin、Guangwei Wang、Mingxing Qian、Eiichi Negishi

  DOI：10.1002/anie.200600012

  日期：2006.4.28