1-三甲基甲硅烷基-5-甲基-1-己炔 | 17906-63-7

• 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
• 中文名称: 1-三甲基甲硅烷基-5-甲基-1-己炔
• 英文名称: trimethyl(5-methylhex-1-yn-1-yl)silane
• 英文别名: 1-trimethylsilyl-5-methyl-1-hexyne；trimethyl-(5-methyl-hex-1-ynyl)-silane；5-methyl-1-trimethylsilanyl-hex-1-yne；Trimethyl(5-methylhex-1-ynyl)silane
• CAS: 17906-63-7
• 化学式: C₁₀H₂₀Si
• 分子量: 168.354
• InChiKey: GIUFYOQXRKYMJN-UHFFFAOYSA-N

物化性质

• 沸点：
  171.5±9.0 °C(Predicted)
• 密度：
  0.790±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 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：

  1-三甲基甲硅烷基-5-甲基-1-己炔 在 氢溴酸 作用下， 生成 2-bromo-5-methyl-hex-1-ene
  参考文献：
  名称：

  Addition of hydrogen bromide to 1-trimethylsilyl-1-alkynes. Convenient synthesis of 2-bromo-1-alkenes

  摘要：

  DOI：

  10.1021/jo00936a042
• 作为产物：
  描述：

  三甲基氯硅烷 、 5-甲基-1-已炔 在 正丁基锂 作用下， 生成 1-三甲基甲硅烷基-5-甲基-1-己炔
  参考文献：
  名称：

  Facile hydroboration of (Z)-1-trimethylsilyl-1-alkenes with dichloroborane–dioxane complex: An easy access to gem-dimetalloalkanes containing boron and silicon

  摘要：

  (Z)-l-Trimethylsilyl-l-alkenes easily prepared by the hydroboration of the corresponding 1-trimethylsilyi-l-alkynes followed by protonolysis with acetic acid, readily react with dichloroborane-dioxane complex in dichloromethane for 6 h. The resulting solution is then treated with 1,3-propane diol in dichloromethane at 0 degrees C for half an hour to provide the corresponding gem-dimetalloalkanes containing boron and silicon. These alpha-trimethylsilylalkylboronate esters are purified by vacuum distillation in high yields (72-84%) and the structures of these novel intermediates are further confirmed by selective oxidation with alkaline hydrogen peroxide to provide the corresponding alcohols containing alpha-trimethylsilyl group in 78-88% isolated yields. (c) 2006 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2005.12.043

文献信息

• A facile stereoselective synthesis of (E)-α-silylvinyl sulfides via hydromagnesiation of alkynylsilanes
  作者：Mingzhong Cai、Jun Xia、Pingping Wang

  DOI：10.1002/hc.20165

  日期：——

  Hydromagnesiation of alkynylsilanes 1 in diethyl ether gave (Z)-α-silylvinyl Grignard reagents 2, which reacted with arylsulfenyl chlorides 3 to afford stereoselectively (E)-α-silylvinyl sulfides 4 in good yields. (E)-α-Silylvinyl sulfides 4 could undergo the cross-coupling reactions with Grignard reagents in the presence of NiCl2(PPh3)2 to give stereoselectively (Z)-1,2-disubstituted vinylsilanes

  炔基硅烷 1 在乙醚中的水镁化作用得到 (Z)-α-甲硅烷基乙烯基格氏试剂 2，其与芳基亚磺酰氯 3 反应以良好的收率立体选择性地提供 (E)-α-甲硅烷基乙烯基硫化物 4。(E)-α-甲硅烷基乙烯基硫化物 4 可以在 NiCl2(PPh3)2 存在下与格氏试剂发生交叉偶联反应，以立体选择性地生成 (Z)-1,2-二取代乙烯基硅烷 5。© 2005 Wiley Periodicals, Inc.杂原子化学 16:644–647, 2005; 在线发表于 Wiley InterScience (www.interscience.wiley.com)。DOI 10.1002/hc.20165
• Catalytic Intermolecular C(sp³)–H Amination: Selective Functionalization of Tertiary C–H Bonds vs Activated Benzylic C–H Bonds
  作者：Erwan Brunard、Vincent Boquet、Elsa Van Elslande、Tanguy Saget、Philippe Dauban

  DOI：10.1021/jacs.1c03872

  日期：2021.5.5

  A catalytic intermolecular amination of nonactivated tertiary C(sp3)–H bonds (BDE of 96 kcal·mol–1) is reported for substrates displaying an activated benzylic site (BDE of 85 kcal·mol–1). The tertiary C(sp3)–H bond is selectively functionalized to afford α,α,α-trisubstituted amides in high yields. This unusual site-selectivity results from the synergistic combination of Rh2(S-tfpttl)4, a rhodium(II)

  据报道，未活化的叔 C(sp 3 )–H 键（BDE 为 96 kcal·mol –1）的催化分子间胺化作用用于显示活性苄基位点（BDE 为 85 kcal·mol –1）的底物。叔 C(sp 3 )-H 键被选择性地官能化以高产率提供 α,α,α-三取代酰胺。这种不寻常的位点选择性是由 Rh 2 ( S -tfpttl) 4与叔丁基苯酚氨基磺酸盐 (TBPhsNH 2)，这导致在温和的氧化条件下区分铑结合的氮烯物种。该催化系统非常稳定，反应以 50 mmol 规模进行，仅使用 0.01 mol % 的催化剂。可以在温和条件下去除 TBPhs 基团，得到相应的不含NH 的胺。
• Activation of carboxylic acids and alcohols by intramolecular cyclization. Acylation of trimethylsilyacetylenes and alkylation of aromatic compounds.
  作者：Satoshi Fukuoka、Hiroshio Nanri、Tsutomu Katsuki、Masaru Yamaguchi

  DOI：10.1016/s0040-4039(00)61847-6

  日期：1987.1

  Carboxylic α-bromo--toluic anhydrides and alkyl α-bromo--toluates were activated by silver salts and used for the acylation of trimethylsilylacetylenes to acetylenic ketones and alkylation of aromatic compounds, respectively.

  羧基α-溴-甲苯酸酐和烷基α-溴-甲苯酸酯被银盐活化，分别用于将三甲基甲硅烷基乙炔酰化为乙炔酮和将芳族化合物烷基化。
• Nickel-catalyzed cross-coupling of primary alkyl halides with phenylethynyl- and trimethylsilyethynyllithium reagents
  作者：Guoqiang Xu、Xiaoyan Li、Hongjian Sun

  DOI：10.1016/j.jorganchem.2011.05.017

  日期：2011.9

  coupling system is described which is promoted by a well-defined and moisture-stable pincer complex [NiClC6H3-2,6-(OPPh2)2}] (1). Non-activated alkyl halides could be efficiently coupled with phenylethynyl- and trimethylsilylethynyllithium reagents at room temperature. Compared to the alkylation of primary alkyl halides with alkynyllithium reagents in literatures, this method requires milder conditions

  描述了一种高效的烷基-炔基偶联体系，该体系由定义明确且耐湿的夹钳络合物[NiCl C 6 H 3 -2,6-（OPPh 2）2 }]（1）促进。未活化的烷基卤化物可以在室温下与苯基乙炔基-和三甲基甲硅烷基乙炔基锂试剂有效偶联。与文献中使用炔基锂试剂将卤代烷基卤化物进行烷基化相比，该方法需要较温和的条件（室温）并且进展迅速。这项研究将使这些易于获得的炔基锂试剂对于有机合成更加有用。
• Novel stereoselective synthesis of 1,3-dienylsilanes via hydromagnesiation reaction of alkynylsilanes
  作者：Mingzhong Cai、Wenyan Hao、Hong Zhao、Caisheng Song

  DOI：10.1016/s0022-328x(03)00461-3

  日期：2003.8

  Hydromagnesiation of alkynylsilanes gives (Z)-α-silylvinyl Grignard reagents, which undergo palladium-catalyzed cross-coupling reactions with alkenyl halides to afford stereoselectively 1,3-dienylsilanes in good yields.

  炔基硅烷的氢镁化反应生成（Z）-α-甲硅烷基乙烯基格氏试剂，其与钯基烯基进行钯催化的交叉偶联反应，从而以良好的收率得到立体选择性的1,3-二烯基硅烷。