methyldiphenyl(phenylethynyl)silane | 129762-91-0

• 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: methyldiphenyl(phenylethynyl)silane
• 英文别名: methyl-diphenyl-(2-phenylethynyl)silane
• CAS: 129762-91-0
• 化学式: C₂₁H₁₈Si
• 分子量: 298.459
• InChiKey: ZGSFSKYTIVPXPQ-UHFFFAOYSA-N

物化性质

• 沸点：
  380.5±15.0 °C(Predicted)
• 密度：
  1.07±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.47
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.05
• 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：

  methyldiphenyl(phenylethynyl)silane 在 palladium diacetate 、 二异丁基氢化铝 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 27.0h， 生成 1,3,5-tris[methyl(diphenyl)silyl]-2-phenylbenzene
  参考文献：
  名称：

  Regioselective Synthesis of Multisubstituted Benzenes by Palladium-Catalyzed Intermolecular Reaction of β-Iodo-β-silylstyrenes with Alkynes

  摘要：

  The Pd-catalyzed reaction between beta-iodo-beta-silyistyrenes and terminal alkynes in i-Pr2NEt gave 1,2,3,5-tetrasubstituted benzenes with complete regioselection. The use of certain silylacetylenes as alkynes enabled efficient synthesis of 1,3,5-trissilyl-2-arylbenzenes, which could be transformed into other multisubstituted benzenes by displacement of the silyl groups.

  DOI：

  10.1021/ol4010883
• 作为产物：
  描述：

  二苯基硅烷 在 [{(DIPP-nacnac)CaH(thf)}2] 作用下， 以 乙醚 、 甲苯 为溶剂， 反应 14.0h， 生成 methyldiphenyl(phenylethynyl)silane
  参考文献：
  名称：

  钙催化的末端炔烃与氢化硅烷的 C(sp)-H 甲硅烷基化

  摘要：

  这项工作报告了通过使用分子氢化钙 [{( DIPP nacnac)CaH(thf)} 2 ] ( DIPP nacnac = CH{(CMe)(2,6- i Pr 2 -C 6 H 3 N)} 2 ) 作为催化剂。该反应选择性地以高分离产率提供单炔基硅烷，具有广泛的底物范围和高原子经济性。进行了对照实验和动力学研究，以提供对催化反应的一些见解。此外，所得炔基硅烷容易衍生形成其他产物。

  DOI：

  10.1016/j.poly.2022.115771

文献信息

• Tuning the Selectivity of AuPd Nanoalloys towards Selective Dehydrogenative Alkyne Silylation
  作者：Maren Wissing、Armido Studer

  DOI：10.1002/chem.201900493

  日期：2019.4.23

  The cross‐dehydrogenative coupling of terminal alkynes and hydrosilanes catalyzed by AuPd nanoalloys is described. Metal nanoparticles are readily prepared in 15 minutes from commercially available and cheap starting materials by using a photochemical approach. The ratio of Au and Pd in the alloys heavily influences their reactivity. These cooperative nanoalloy catalysts tolerate a large number of

  描述了AuPd纳米合金催化的末端炔烃和氢硅烷的交叉脱氢偶联。通过使用光化学方法，可以容易地在15分钟内从可商购的廉价原材料制备金属纳米颗粒。合金中金和钯的比例严重影响了它们的反应性。这些协同纳米合金催化剂可耐受大量官能团（例如，游离胺和酸），可在室温下在空气气氛下以低负荷（2摩尔％）运行，并且交叉脱氢偶联可轻松扩大规模。
• Vinylgallium and Alkyllithium Compounds: Transmetalation and Generation of Oligolithium Cages
  作者：Werner Uhl、Dirk Kovert、Marcus Layh、Alexander Hepp

  DOI：10.1002/chem.201102057

  日期：2011.11.25

  Vinylgallium compounds [C6H6−n(H)CC(SiR2R′)GaR′′2}n] (3, R=Ph, Me; R′=Ph, Me; R′′=tBu, Et; n=1, 2) are easily accessible by hydrogallation of the corresponding alkynylbenzene derivatives with HGaCl2 and subsequent reaction with alkyllithium derivatives. Treatment of 3 with an excess amount of tert‐butyl‐ or ethyllithium yielded by transmetalation and ortho‐deprotonation of the aromatic rings the

  Vinylgallium化合物[C 6 H ^ 6- Ñ （H）CC（SIR 2 R'） GAR'' 2 } Ñ ]（3，R =苯基中，Me; R'=苯基中，Me; R''=吨丁基，乙基; ñ = 1，2）是通过用H相应alkynylbenzene衍生物hydrogallation方便的GaCl 2并用烷基锂衍生物随后的反应。的治疗3与过量叔通过转移金属化，得到丁基-或乙基锂和邻位的芳族环的-deprotonation前所未有无溶剂oligolithium簇化合物[（C6 H 4 Li）HCC（SiPh 3）Li} 2（t BuLi）2 ]（4），[（C 6 H 4 Li）HCC（SiPh 2 Me）Li} 4 ]（5）和[（C 6 H 3 Li）HCC（SiMe 3）Li} 2 } 3 ]（6）的收率中等。它们的固态结构表明存在具有6、8或9个锂原子的独特分子锂簇，这些簇可能源自两个边缘共享的Li
• Dehydrogenative Silylation of Terminal Alkynes with Hydrosilanes under Zinc-Pyridine Catalysis
  作者：Teruhisa Tsuchimoto、Masakazu Fujii、Yoshihiko Iketani、Masaru Sekine

  DOI：10.1002/adsc.201200310

  日期：2012.11.12

  A combination of zinc triflate and pyridine in a nitrile medium was found to act as an effective catalytic system for dehydrogenative silylation with flexible pieces of terminal alkynes and hydrosilanes, thereby producing diverse alkynylsilanes in high to excellent yields.

  发现三氟甲磺酸锌和吡啶在腈介质中的组合可作为有效的催化体系，用于与末端炔烃和氢硅烷的柔性片段进行脱氢甲硅烷基化，从而以高到极好的收率生产各种炔基硅烷。
• Base-mediated one-pot synthesis of alkynylsilanes from terminal alkynes and chlorosilanes
  作者：Jianyang Chen、Hongmei Fu、Huamei He、Shuting Liang、Xiaofeng Luo

  DOI：10.1016/j.tet.2024.133823

  日期：2024.2

  An efficient one-pot method has been developed to synthesize alkynylsilanes from terminal alkynes by treatment with chlorosilanes and LiN(SiMe3)2. The reaction proceeded smoothly at room temperature, showing a broad substrate scope and good functional group tolerance. The practical application was demonstrated by gram-scale reaction.

  开发了一种有效的一锅法，通过用氯硅烷和LiN(SiMe 3 ) 2处理从末端炔烃合成炔基硅烷。反应在室温下顺利进行，表现出广泛的底物范围和良好的官能团耐受性。通过克级反应证明了其实际应用。
• Unexpected Formation of Ga₄C₂H₄ Heteroadamantane Cages by the Reaction of Carbon-Bridged Bis(dichlorogallium) Compounds with <i>tert</i>-Butyllithium
  作者：Werner Uhl、Dirk Kovert、Sarina Zemke、Alexander Hepp

  DOI：10.1021/om200573g

  日期：2011.9.12

  Reactions of the carbon-bridged bis(dichlorogallium) compounds (Cl2Ga)(2)C(SiR2R')-CH2-Ph (1a, R = R' = Me; 1b, R = Ph, R' = Me; 1c, R = Me, R' = CMe3) with four equivalents of tert-butyllithium yielded bis[tert-butyl(hydrido)digallium] compounds [(Me3C)(H)Ga](2)C(SiR2R')-CH2-Ph}(2) (3a to 3c), via beta-elimination and release of isobutene. 3a to 3c are dimeric in solution and the solid state and contain unprecedented Ga4C2H4 heteroadamantane structures in which four metal atoms are bridged by four hydrogen and two carbon atoms. In contrast, n-propyllithium gave the monomeric tetra(n-propyl)digallium compound ((Pr2Ga)-Pr-n)(2)C(SiMe3)-CH2-Ph (2) under similar conditions, which has two coordinatively unsaturated gallium atoms and may be applicable as a chelating Lewis acid.