(E)-1,4-bis(benzyldimethylsilyl)-1-buten-3-yne | 857350-25-5

• 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: (E)-1,4-bis(benzyldimethylsilyl)-1-buten-3-yne
• 英文别名: (E)-1-(benzyldimethylsilyl)-1-buten-3-yne；benzyl-[(E)-4-[benzyl(dimethyl)silyl]but-1-en-3-ynyl]-dimethylsilane
• CAS: 857350-25-5
• 化学式: C₂₂H₂₈Si₂
• 分子量: 348.635
• InChiKey: FYXUOOJAYNDOQM-GZTJUZNOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.61
• 重原子数：
  24
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 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：

  (E)-1,4-bis(benzyldimethylsilyl)-1-buten-3-yne 在 甲醇 、 t-Bu₃P*Pt(DVDS) 、 potassium trimethylsilonate 、 sodium methylate 、 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 xylene 为溶剂， 反应 13.0h， 生成 (E,E)-[4-(1-naphthyl)-1,3-butadienyl]dimethylbenzylsilane
  参考文献：
  名称：

  Sequential Cross-Coupling of 1,4-Bissilylbutadienes:  Synthesis of Unsymmetrical 1,4-Disubstituted 1,3-Butadienes

  摘要：

  A mild and general and stereospecific cross-coupling reaction of unsymmetrical 1,4-bissilyl-1,3-butadienes has been accomplished. By the use of either a benzyldimethylsilyl or 2-thienyldimethylsilyl unit at one end of the dienylsilanol, a selective cross-coupling could be effected under mildly basic conditions (KOTMS) to afford 4-aryl-1,3-dienylsilanes in excellent yield for a wide range of aryl and alkenyl coupling partners. The second cross-coupling could be effected cleanly by the action of TBAF with electron-rich or electron-poor halides. The sequential process could be telescoped into a "one pot" procedure with overall excellent yields of the unsymmetrical 1,4-diaryl-1,3-butadienes.

  DOI：

  10.1021/ja0518373
• 作为产物：
  描述：

  苄基二甲基氯硅烷 在 Wilkinson's catalyst 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 51.0h， 生成 (E)-1,4-bis(benzyldimethylsilyl)-1-buten-3-yne
  参考文献：
  名称：

  Sequential Cross-Coupling of 1,4-Bissilylbutadienes:  Synthesis of Unsymmetrical 1,4-Disubstituted 1,3-Butadienes

  摘要：

  A mild and general and stereospecific cross-coupling reaction of unsymmetrical 1,4-bissilyl-1,3-butadienes has been accomplished. By the use of either a benzyldimethylsilyl or 2-thienyldimethylsilyl unit at one end of the dienylsilanol, a selective cross-coupling could be effected under mildly basic conditions (KOTMS) to afford 4-aryl-1,3-dienylsilanes in excellent yield for a wide range of aryl and alkenyl coupling partners. The second cross-coupling could be effected cleanly by the action of TBAF with electron-rich or electron-poor halides. The sequential process could be telescoped into a "one pot" procedure with overall excellent yields of the unsymmetrical 1,4-diaryl-1,3-butadienes.

  DOI：

  10.1021/ja0518373

文献信息

• Tandem Nickel-Catalyzed Dimerization/(4+2) Cycloaddition of Terminal Alkynes with Four-Membered Ring Ketones
  作者：Christophe Aïssa、Manuel Barday、Eva Nicolas、Bradley Higginson、François Delmotte、Martin Appelmans

  DOI：10.1055/a-1671-8497

  日期：2022.2

  Controlling the behavior of terminal alkynes in metal-catalyzed intermolecular tandem reactions is a formidable challenge despite the potential advantage offered by these strategies in modern synthesis. Herein, we describe that a nickel catalyst enables a tandem process involving the rapid dimerization of terminal alkynes into 1,3-enynes and the cycloaddition of these intermediates with an azetidinone

  尽管这些策略在现代合成中具有潜在优势，但在金属催化的分子间串联反应中控制末端炔烃的行为是一项艰巨的挑战。在此，我们描述了镍催化剂能够实现串联过程，该过程涉及末端炔烃快速二聚为 1,3-烯炔，以及这些中间体与氮杂环丁酮、氧杂环丁酮或苯并环丁烯酮的环加成反应。重要的是，不需要缓慢或连续添加试剂和催化剂来协调它们的反应性。这些结果与之前带有应变四元环底物的末端炔烃的环加成形成鲜明对比，后者导致低聚或环三聚，但叔丁基乙炔除外。
• An Additive-Free, Base-Catalyzed Protodesilylation of Organosilanes
  作者：Wubing Yao、Rongrong Li、Huajiang Jiang、Deman Han

  DOI：10.1021/acs.joc.7b03139

  日期：2018.2.16

  We report an additive-free, base-catalyzed C–, N–, O–, and S–Si bond cleavage of various organosilanes in mild conditions. The novel catalyst system exhibits high efficiency and good functional group compatibility, providing the corresponding products in good to excellent yields with low catalyst loadings. Overall, this transition-metal-free process may offer a convenient and general alternative to

  我们报道了在温和条件下各种有机硅烷的无添加剂，碱催化的C–，N–，O–和S–Si键断裂。该新型催化剂体系表现出高效率和良好的官能团相容性，以较低的催化剂载量提供相应的产物，收率良好至优异。总的来说，这种无过渡金属的方法可以为目前使用过量的碱，强酸或金属催化的系统进行有机硅烷的原甲硅烷基化提供一种方便且通用的替代方法。