2-环己基乙炔基(三甲基)硅烷 | 66270-60-8

• 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: 2-环己基乙炔基(三甲基)硅烷
• 英文名称: (cyclohexylethynyl)trimethylsilane
• 英文别名: 1-trimethylsilyl-2-cyclohexylacetylene；(Cyclohexylethynyl)(trimethyl)silane；2-cyclohexylethynyl(trimethyl)silane
• CAS: 66270-60-8
• 化学式: C₁₁H₂₀Si
• 分子量: 180.365
• InChiKey: CRBYBEHYDAJKDP-UHFFFAOYSA-N

物化性质

• 沸点：
  82-83 °C(Press: 7 Torr)
• 密度：
  0.85±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.45
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 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：

  2-环己基乙炔基(三甲基)硅烷 在 sodium hydroxide 作用下， 以 甲醇 为溶剂， 反应 24.0h， 以94%的产率得到环己基乙炔
  参考文献：
  名称：

  Chiral synthesis via organoboranes. 29. A general synthesis of .alpha.-chiral monosubstituted acetylenes and their trimethylsilyl derivatives from enantiomerically pure boronic esters

  摘要：

  The procedure for the synthesis of RC = CH by the iodination of [R3BC = CH]-Li+ is impractical for the synthesis of the corresponding chiral derivatives, R*C = CH, due to the unavailability of the required R*3B compounds. RThxBOMe and R*ThxBOCH3, now readily available by established procedures, serve handily for the syntheses of RC = CR' and R*C = CR respectively from LiC = CR, but fail for the syntheses of either RC = CH or R*C = CH, in reasonable yield, from LiC = CH. Fortunately, this difficulty can be circumvented by utilizing LiC = CSiMe3. Indeed, treatment of enantiomerically pure monoalkylthexylborinates, R*ThxBOCH3, readily prepared from enantionerically pure boronic esters, with LiC = CSiMe3 forms an ate complex which readily undergoes the desired iodine-induced rearrangement, forming alpha-chiral (trimethylsilyl)acetylenes, R*C = CSiMe3. The (trimethylsilyl)acetylenes are easily desilylated to afford the corresponding alpha-chiral terminal acetylenes, R*C = CH, in yields of approximately 70% and essentially 100% enantiomeric excess (greater-than-or-equal-to 99%). These intermediates, R*C = CSiMe3 and R*C = CH, can be readily converted by simple procedures into a wide variety of pure enantiomers: R*CH = CH2, R*CH2CHO, R*CO2H, R*CH2CO2H, R*COCO2R, etc. Since both (+)- and (-)-alkylboronic esters are now readily available in essentially 100% enantiomeric purity, it is now possible to synthesize (+)- and (-)-alpha-chiral monosubstituted acetylenes and their trimethylsilyl derivatives in very high enantiomeric purities. This provides the first general, efficient synthesis of these valuable synthons in such high enantiomeric purities.

  DOI：

  10.1021/jo00004a030
• 作为产物：
  描述：

  ((1-甲氧基环己基)乙炔基)三甲基硅烷 在 正丁基锂 、 二氯二茂锆 、 盐酸 、 水 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以55%的产率得到2-环己基乙炔基(三甲基)硅烷
  参考文献：
  名称：

  烯丙基/炔丙基锆配合物的产生及随后的交叉偶联反应：多取代烯的简便合成

  摘要：

  炔丙基醚与Negishi试剂的β-醇盐消除反应在水解后会生成丙二烯和/或炔烃。产物的分布高度取决于起始炔丙基醚的取代方式。也就是说，芳基或烷基取代的炔丙基醚有利于丙二烯产物，而TMS取代的炔丙基醚则可提供炔烃。DFT计算显示，TMS组的大位阻效应和β效应均有利于炔烃产物，从而逆转了选择性。烯丙基/炔丙基锆中间体与芳基碘化物在Pd（PPh 3）4 / CuCl存在下的随后偶联反应为合成多取代的烯烯提供了一条直接途径。

  DOI：

  10.1021/jo9020419

文献信息

• Mild and Phosphine-Free Iron-Catalyzed Cross-Coupling of Nonactivated Secondary Alkyl Halides with Alkynyl Grignard Reagents
  作者：Chi Wai Cheung、Peng Ren、Xile Hu

  DOI：10.1021/ol501087m

  日期：2014.5.2

  cross-coupling of nonactivated secondary alkyl bromides and iodides with alkynyl Grignard reagents at room temperature has been developed. A wide range of secondary alkyl halides and terminal alkynes are tolerated to afford the substituted alkynes in good yields. A slight modification of the reaction protocol also allows for cross-coupling with a variety of primary alkyl halides.

  已经开发出一种简单的方案，用于在室温下将非活化的仲烷基溴化物和碘化物与炔基格氏试剂进行铁催化的交叉偶联。宽范围的仲烷基卤化物和末端炔烃是可接受的，以高收率提供了取代的炔烃。反应方案的略微修改也允许与多种伯烷基卤化物交叉偶联。
• γ-Carboline synthesis enabled by Rh(<scp>iii</scp>)-catalysed regioselective C–H annulation
  作者：Bo Jiang、Jingwen Jia、Yufei Sun、Yichun Wang、Jing Zeng、Xiubin Bu、Liangliang Shi、Xiaoying Sun、Xiaobo Yang

  DOI：10.1039/d0cc04740f

  日期：——

  A Rh(iii)-catalysed C–H annulation of indolyl oximes with alkynyl silanes was developed, delivering diverse γ-carbolines with unexpected reverse regioselectivity.

  通过Rh(iii)催化的indolyl oximes与炔基硅烷的C-H环化反应已经开发成功，产生多样的γ-咔啉类化合物，具有意外的反向区域选择性。
• Triethylborane-induced radical addition of alkyl iodides to acetylenes
  作者：Yoshifumi Ichinose、Shin-ichiro Matsunaga、Keigo Fugami、Koichiro Oshima、Kiitiro Utimoto

  DOI：10.1016/s0040-4039(00)99189-5

  日期：——

  Treatment of terminal acetylenes (R1CCH) with secondary or tertiary alkyl iodides (R2I) in the presence of triethylborane provides the corresponding alkenyl iodides (R1C(I)CHR2) in good yields.

  在三乙基硼烷的存在下，用仲或叔烷基碘（R 2 I）处理末端乙炔（R 1 C = CH）可得到相应的烯基碘（R 1 C（I）= CHR 2）。
• Cobalt-Mediated Cross-Coupling Reactions of Primary and Secondary Alkyl Halides with 1-(Trimethylsilyl)ethenyl- and 2-Trimethylsilylethynylmagnesium Reagents
  作者：Hirohisa Ohmiya、Hideki Yorimitsu、Koichiro Oshima

  DOI：10.1021/ol0611144

  日期：2006.7.1

  [reaction: see text] This paper describes cobalt-mediated cross-coupling reactions of alkyl halides with 1-(trimethylsilyl)ethenylmagnesium bromide and 2-(trimethylsilyl)ethynylmagnesium bromide, respectively. The cobalt system allows for employing secondary as well as primary alkyl halides as the substrates. The reactions offer facile formations of alkyl-alkenyl and alkyl-alkynyl bonds. The reaction

  [反应：见正文]本文分别描述了烷基卤化物与1-（三甲基甲硅烷基）乙烯基溴化镁和2-（三甲基甲硅烷基）乙炔基溴化镁的钴介导的交叉偶联反应。钴系统允许使用仲烷基卤和伯烷基卤作为底物。反应提供了容易形成的烷基-烯基和烷基-炔基键。反应机理将包括从钴配合物到卤代烷的单电子转移，以产生相应的烷基。钴系统因此使得6-卤代-1-己烯衍生物的顺序的自由基环化/烯基化和环化/炔基化反应成为可能。
• Aluminum-Catalyzed Selective Hydroboration of Alkenes and Alkynylsilanes
  作者：Feng Li、Xu Bai、Yuan Cai、Han Li、Shuo-Qing Zhang、Feng-Hua Liu、Xin Hong、Youjun Xu、Shi-Liang Shi

  DOI：10.1021/acs.oprd.9b00205

  日期：2019.8.16

  An efficient aluminum-catalyzed selective hydroboration of alkenes and alkynylsilanes is reported. A wide variety of alkenes and alkynylsilanes bearing various functional groups and heterocyclic substituents were converted to boronic ester products in good yields with high selectivity. Mechanistically, density functional theory calculations favored a mechanism involving the insertion of the double

  报道了铝和炔基硅烷的铝的有效催化的选择性硼氢化。带有各种官能团和杂环取代基的各种各样的烯烃和炔基硅烷以高收率和高选择性被转化为硼酸酯产物。从机理上讲，密度泛函理论的计算偏向于一种机制，该机制涉及将双键插入Al–H物种，然后进行C–Al / B–H复分解。