(E)-1,4-bis(tert-butyldimethylsilyl)but-1-en-3-yne | 126615-06-3

• 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: (E)-1,4-bis(tert-butyldimethylsilyl)but-1-en-3-yne
• 英文别名: (e)-1,4-Bis(t-butyl-dimethylsilyl)but-1-en-3-yn；tert-butyl-[(E)-4-[tert-butyl(dimethyl)silyl]but-1-en-3-ynyl]-dimethylsilane
• CAS: 126615-06-3
• 化学式: C₁₆H₃₂Si₂
• 分子量: 280.601
• InChiKey: JMNFRWIJELOQNJ-ACCUITESSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.64
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 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(tert-butyldimethylsilyl)but-1-en-3-yne 在 N-碘代丁二酰亚胺 作用下， 以 六氟异丙醇 为溶剂， 以91%的产率得到(E)-4-tert-butyldimethylsilyl-1-iodo-1-buten-3-yne
  参考文献：
  名称：

  Iododesilylation of TIPS-, TBDPS-, and TBS-Substituted Alkenes in Connection with the Synthesis of Amphidinolides B/D

  摘要：

  The C-Si bonds of triisopropylsilyl-substituted alkenes, 1,3-dienes, and related multifunctional substrates, as well as analogous C-TBDPS and C-TBS bonds, are readily and chemoselectively cleaved with NIS (or other sources of I(+), such as N-iodosaccharin, 1,3-diodohydantoin, and Ipy(2)BF(4)). The desired iodoalkenes are obtained stereospecifically without byproducts, provided that the reactions are carried out in CF(3)CHOHCF(3) and, in general, with 30 mol % of Ag(2)CO(3) (or AgOAc/2,6-Iutidine) as an additive. Fragment C10-C18 of cytotoxic amphidinolides B1-B3 and D has been synthesized using this improved procedure.

  DOI：

  10.1021/ol2020187
• 作为产物：
  描述：

  (叔丁基二甲基)乙炔 在 [{Pd(μ-OH)Cl(1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene)}₂] 、 potassium hydroxide 作用下， 以 甲苯 为溶剂， 反应 2.0h， 以98%的产率得到(E)-1,4-bis(tert-butyldimethylsilyl)but-1-en-3-yne
  参考文献：
  名称：

  在PEPPSI预催化剂和相对的氯桥基和羟基桥联的N-杂环卡宾钯二聚体存在下，末端乙炔的选择性二聚

  摘要：

  在[PdCl 2（IPr）（3-氯吡啶）]，PEPPSI预催化剂家族的其他成员以及与结构相关的N杂环卡宾钯二聚体，即[{ PdCl 2（IPr）（3-氯吡啶）]存在下，末端乙炔的高度区域和立体选择性二聚发生（μ–Cl）Cl（IPr）} 2 ]和[{Pd（μ–OH）Cl（IPr）} 2 ]（IPr = 1,3-双（2,6-二异丙基苯基）咪唑-2-亚烷基）。该反应导致头对头二聚产物的E-异构体的排他性形成。[{Pd（μ–OH）Cl（IPr）} 2 ]在室温下催化宽范围的芳基和甲硅烷基乙炔的二聚作用，并且能够在无碱条件下起作用。

  DOI：

  10.1016/j.jorganchem.2017.12.041

文献信息

• Five-membered zircona- and titanacycloallenes; their diverse reactivity depending upon the position of substituents
  作者：Noriyuki Suzuki、Rikako Kurita、Akiko Kawamura、Tomoyuki Ono、Yoshiro Masuyama

  DOI：10.1016/j.jorganchem.2018.08.010

  日期：2018.11

  Five-membered metallacycloallene compounds that are 2,5-disubstituted 1-zirconacyclopenta-2,3-dienes were prepared from (E)-1,4-bis(trialkylsilyl)but-1-en-3-ynes in good yields. The structures of these compounds were determined by X-ray diffraction study. Contrary to our previous study on 2,4-disubstituted 1-zirconacyclopenta-2,3-dienes, which gave alkynyl alcohols by the reaction with ketones after

  由（E）-1,4-双（三烷基甲硅烷基）but-1-en-3-ynes以良好的收率制备了2,5-二取代的1-氧化锆环戊基-2,3-二烯的五元金属杂环化合物。这些化合物的结构通过X射线衍射研究确定。与我们之前对2,4-二取代的1-zrconacyclopenta-2,3-二烯的研究相反，后者在水解后与酮反应生成炔醇，而2,5-双（三烷基甲硅烷基）配合物与酮反应生成烯丙醇。与腈的反应可能通过形成七元的1-氮杂-2-氧化锆环庚-3、4、7-三烯环结构而生成吡咯化合物。用异丙醇钛/ n处理（E）-1,4-双（三烷基甲硅烷基）but-1-en-3-ynes丁基锂，然后与腈反应，得到相应的炔基酮。
• Synthesis and reactions of (E)-1,4-bis(silyl)-substituted enynes
  作者：Joji Ohshita、Kenji Furumori、Akira Matsuguchi、Mitsuo Ishikawa

  DOI：10.1021/jo00297a054

  日期：1990.5
• Regio- and Stereoselective Homodimerization of Monosubstituted Acetylenes in the Presence of the Second Generation Grubbs Catalyst
  作者：Beata Powała、Cezary Pietraszuk

  DOI：10.1007/s10562-013-1134-z

  日期：2014.3

  Silyl- and phenylacetylenes undergo efficient homodimerization in the presence of a second generation Grubbs catalyst. The reaction permits fully regio- and stereoselective synthesis of disubstituted 1,3-enynes. The other commonly used ruthenium-based olefin metathesis catalysts remain inactive in the reaction.
• Iododesilylation of TIPS-, TBDPS-, and TBS-Substituted Alkenes in Connection with the Synthesis of Amphidinolides B/D
  作者：Mireia Sidera、Anna M. Costa、Jaume Vilarrasa

  DOI：10.1021/ol2020187

  日期：2011.9.16

  The C-Si bonds of triisopropylsilyl-substituted alkenes, 1,3-dienes, and related multifunctional substrates, as well as analogous C-TBDPS and C-TBS bonds, are readily and chemoselectively cleaved with NIS (or other sources of I(+), such as N-iodosaccharin, 1,3-diodohydantoin, and Ipy(2)BF(4)). The desired iodoalkenes are obtained stereospecifically without byproducts, provided that the reactions are carried out in CF(3)CHOHCF(3) and, in general, with 30 mol % of Ag(2)CO(3) (or AgOAc/2,6-Iutidine) as an additive. Fragment C10-C18 of cytotoxic amphidinolides B1-B3 and D has been synthesized using this improved procedure.
• Selective dimerization of terminal acetylenes in the presence of PEPPSI precatalysts and relative chloro- and hydroxo-bridged N -heterocyclic carbene palladium dimers
  作者：Sylwia Ostrowska、Natalia Szymaszek、Cezary Pietraszuk

  DOI：10.1016/j.jorganchem.2017.12.041

  日期：2018.2

  Highly regio- and stereoselective dimerization of terminal acetylenes occurs in the presence of [PdCl2(IPr)(3-chloropyridine)], other members of the family of PEPPSI precatalysts and the structurally related N-heterocyclic carbene palladium dimers, i.e. [Pd(μ–Cl)Cl(IPr)}2] and [Pd(μ–OH)Cl(IPr)}2] (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene). The reaction leads to exclusive formation of

  在[PdCl 2（IPr）（3-氯吡啶）]，PEPPSI预催化剂家族的其他成员以及与结构相关的N杂环卡宾钯二聚体，即[ PdCl 2（IPr）（3-氯吡啶）]存在下，末端乙炔的高度区域和立体选择性二聚发生（μ–Cl）Cl（IPr）} 2 ]和[Pd（μ–OH）Cl（IPr）} 2 ]（IPr = 1,3-双（2,6-二异丙基苯基）咪唑-2-亚烷基）。该反应导致头对头二聚产物的E-异构体的排他性形成。[Pd（μ–OH）Cl（IPr）} 2 ]在室温下催化宽范围的芳基和甲硅烷基乙炔的二聚作用，并且能够在无碱条件下起作用。