(Z)-1-bromo-4-trimethylsilyl-1-buten-3-yne | 181214-47-1

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (Z)-1-bromo-4-trimethylsilyl-1-buten-3-yne
• 英文别名: [(Z)-4-bromobut-3-en-1-ynyl]-trimethylsilane
• CAS: 181214-47-1
• 化学式: C₇H₁₁BrSi
• 分子量: 203.154
• InChiKey: HLZBLUKDUBOQPX-XQRVVYSFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.78
• 重原子数：
  9
• 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：

  苯乙炔 、 (Z)-1-bromo-4-trimethylsilyl-1-buten-3-yne 在 copper(l) iodide 、 四(三苯基膦)钯 二异丙胺 作用下， 以 苯 为溶剂， 反应 0.17h， 生成 trimethyl[(3Z)-6-phenylhex-3-ene-1,5-diynyl]silane
  参考文献：
  名称：

  Palladium-Catalyzed Stereoselective Hydrogenolysis of Conjugated 1,1-Dibromo-1-alkenes to (Z)-1-Bromo-1-alkenes. An Application to Stepwise and One-Pot Synthesis of Enediynes and Dienynes

  摘要：

  DOI：

  10.1021/jo961013r
• 作为产物：
  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

文献信息

• A stereoselective synthesis of silylated polyunsaturated halides from α,β-epoxysilanes
  作者：Francesco Babudri、Vito Fiandanese、Giuseppe Marchese、Angela Punzi

  DOI：10.1016/s0040-4020(00)01010-3

  日期：2001.1

  has been developed, starting from the readily available (1E,3E)-1,4-bis(trimethylsilyl)-1,3-butadiene and (3E)-1,4-bis(trimethylsilyl)-3-buten-1-yne. A simple epoxidation reaction, followed by regioselective α-opening of the epoxide ring by metal halides affords the corresponding halohydrins with a high degree of stereoselectivity. A subsequent β-elimination reaction from these compounds leads to (Z

  从容易获得的（1 E，3 E）-1,4-双（三甲基甲硅烷基）-1,3-丁二烯和（3 E）-1,4-bis开始开发了一种新的合成方法来硅烷化多不饱和卤化物（三甲基甲硅烷基）-3-丁烯-1-炔。简单的环氧化反应，然后通过金属卤化物对环氧环进行区域选择性α-开环，可得到具有高度立体选择性的相应卤代醇。这些化合物随后的β-消除反应导致（Z，E）-二烯基卤化物和（Z）-烯炔卤化物。
• Stereoselective Hydrogenolysis of 1,1-Dibromo-1-alkenes and Stereospecific Synthesis of Conjugated (<i>Z</i>)-Alkenyl Compounds
  作者：Jun'ichi Uenishi、Reiko Kawahama、Osamu Yonemitsu、Jiro Tsuji

  DOI：10.1021/jo9812781

  日期：1998.11.1

  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.
• Palladium-Catalyzed Stereoselective Hydrogenolysis of Conjugated 1,1-Dibromo-1-alkenes to (<i>Z</i>)-1-Bromo-1-alkenes. An Application to Stepwise and One-Pot Synthesis of Enediynes and Dienynes
  作者：Jun'ichi Uenishi、Reiko Kawahama、Osamu Yonemitsu、Jiro Tsuji

  DOI：10.1021/jo961013r

  日期：1996.1.1