(Z)-2-(trimethylsilyloxy)but-2-ene

• 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: (Z)-2-(trimethylsilyloxy)but-2-ene
• 英文别名: 2-(trimethylsilyloxy)-(Z)-2-butene；[(Z)-but-2-en-2-yl]oxy-trimethylsilane
• 化学式: C₇H₁₆OSi
• 分子量: 144.289
• InChiKey: MFSRVRADAQZHSP-SREVYHEPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.76
• 重原子数：
  9
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  6-(氯甲酸基)己炔羧酸乙酯 、 (Z)-2-(trimethylsilyloxy)but-2-ene 在 zinc(II) chloride 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成 ethyl 7,9-dioxo-8-methyldecanoate
  参考文献：
  名称：

  Novel Linear Tetrapyrroles: Hydrogen Bonding in Diacetylenic Bilirubins

  摘要：

  Bilirubin congeners with dipyrrinones conjoined to a diaceteylene unit (-Cequivalent toC-Cequivalent toC-) rather than to -CH2- were synthesized and examined spectroscopically. This new class of rubrified linear tetrapyrroles cannot easily fold or bend in the middle, but the dipyrrinones can rotate independently about the diacetylene unit. Thus, unlike bilirubin, which is bent in the middle and has a ridge-tile shape, the diacetylene unit orients the attached dipyrrinones along a linear path, and intramolecular hydrogen bonding between the dipyrrinones and opposing carboxylic acids preserves a twisted linear molecular shape when the usual propionic acids are replaced by hexanoic. In a bis-hexanoic acid rubin, the extended planes of the dipyrrinones intersect along the -(Cequivalent toC)(2)- axis at an angle of 102degrees for the conformation stabilized by intramolecular hydrogen bonding. With propionic acid chains, however, neither CO2H can engage an opposing dipyrrinone in intramolecular hydrogen bonding, and the energy-minimum conformation of this linear pigment, shows nearly co-planar dipyrrinones, with an intersection of an angle of similar to180degrees of the extended planes of the dipyrrinones. Spectroscopic evidence for such linearized and twisted (bis-hexanoic) and planar (bis-propionic) structures comes from the pigments' NMR spectral data and their exciton UV-Vis and induced circular dichroism spectra.

  DOI：

  10.1007/s00706-003-0157-3
• 作为产物：
  描述：

  550.0 ℃ 、66.66 Pa 条件下， 生成 (Z)-2-(trimethylsilyloxy)but-2-ene
  参考文献：
  名称：

  一些烯基三甲基硅烷转化为甲硅烷基烯醇醚

  摘要：

  烯基三甲基硅烷和乙腈氧化物之间的环加成产物（5-三甲基甲硅烷基恶唑啉）进行热解重排-环还原，得到相对于起始烯基硅烷而言保留立体化学的甲硅烷基烯醇醚。

  DOI：

  10.1016/s0022-328x(00)85675-2

文献信息

• A new practical synthesis of silyl enol ethers
  作者：P. Cazeau、F. Duboudin、F. Moulines、O. Babot、J. Dunogues

  DOI：10.1016/s0040-4020(01)86789-2

  日期：1987.1

  A new, practical route to enoxysilanes is described from simple enolizable aldehydes or ketones, using the trimethylchlorosilane-sodium iodide—tertiary amine reagent in acetonitrile. From certain aldehydes, an onium intermediate has been isolated. A conformational study of this onium intermediate and a thermal unimolecular syn-elimination process may explain the stereoselectivity of the reaction. Such

  描述了一种新的实用的方法，使用三甲基氯硅烷-碘化钠-叔胺试剂在乙腈中，由简单的可烯化的醛或酮制得环氧乙烷。从某些醛中，已分离出一种中间体。对这种鎓中间体和热单分子同消去过程的构象研究可以解释该反应的立体选择性。这样的解释可以扩展到所考虑的所有醛和酮。与羰基衍生物和胺的性质有关的立体因素对反应的区域和立体控制起着至关重要的作用。
• Sur l'obtention hautement regio-et stereoselective d'enoxysilanes par action du bis(trimethylsilyl) acetamide en milieu hmpt sur les derives carbonyles enolisables
  作者：James Dedier、Pierre Gerval、Emile Frainnet

  DOI：10.1016/s0022-328x(00)85896-9

  日期：1980.2

  The authors describe a new and general method for the preparation of enoxysilanes by silylation of enolizable aldehydes and ketones by use of bis(trimethylsilyl) acetamide in HMPT, in the presence of very small quantities of sodium metal(or another basic agent) as catalyst. This method was found to proceed rapidly, with good yields, and is highly regio-and stereo-selective (giving the Z isomer, orientation

  作者描述了一种新的通用方法，该方法是在非常少量的钠金属（或另一种碱性试剂）存在的情况下，通过在HMPT中使用双（三甲基甲硅烷基）乙酰胺对可烯化的醛和酮进行甲硅烷基化来制备环氧硅烷。发现该方法快速进行，具有良好的产率，并且是高度区域选择性和立体选择性的（给出Z异构体，由动力学控制产生取向）。提出了这种反应的机理以及对观察到的区域选择性和立体选择性的解释。
• Characterization of covalent Ene adduct intermediates in “hydride equivalent” transfers in a dihydropyridine model for NADH reduction reactions
  作者：R. Daniel Libby、Ryan A. Mehl

  DOI：10.1016/j.bioorg.2011.10.002

  日期：2012.2

  compounds has produced the first direct evidence for an obligatory covalent adduct between a dihydropyridine and substrate in a reduction reaction. The reactions were monitored by NMR spectroscopy. In all reactions studied, the covalent adduct was the first new species detected and its decomposition to form products could be observed. Concentrations of adducts were sufficiently high at steady-state

  对NADH模型1,4-二（三甲基甲硅烷基）-1,4-二氢吡啶7与一系列α，β-不饱和氰基和羰基化合物的反应的研究为强制性共价提供了第一个直接证据在还原反应中二氢吡啶与底物之间的加合物。通过NMR光谱监测反应。在所有研究的反应中，共价加合物是第一个检测到的新物种，并且可以观察到其分解生成产物。加合物的浓度在稳态下足够高，可以直接从反应混合物的NMR光谱中确定其结构。加合物结构是由7与底物之间的Ene反应所预期的那些。该第一反应步骤导致C 4的转移氢原子与底物7形成氢原子，并在二氢吡啶环的C 2与底物α原子之间形成共价键。这些烯加合物中间体的发现完善了在NADH模型反应中观察到的机制范围，从而涵盖了具有自由基中间体，没有可检测的中间体和现在的共价中间体的那些机理。将形成Ene加合物的过渡态的几何形状与理论过渡态模型的几何形状和酶-底物/抑制剂复合物的晶体结构进行比较，以表明二氢吡啶环和底物处于
• A Practical Method for the Preparation of Trimethylsilyl Enol Ethers
  作者：Ji-Mao Lin、Ben-Sheng Liu

  DOI：10.1080/00397919708004194

  日期：1997.3

  Abstract In the mixed system of chlorotrimethylsilane/triethyl amine/N,N-dimethylformamide/potassium iodide/petroleum ether, aldehydes or ketones are silylated to silyl enol ethers at room temperature. The N,N-dimethylformamide / potassium iodie layer can be used as circulating liquor for many times. The yields are high.

  摘要 在三甲基氯硅烷/三乙胺/N,N-二甲基甲酰胺/碘化钾/石油醚的混合体系中，醛或酮在室温下被硅烷化为甲硅烷基烯醇醚。N,N-二甲基甲酰胺/碘化钾层可多次用作循环液。产量很高。
• A stereoselective isomerization of allyl silyl ethers to (E)- or (Z)-silyl enol ethers using cationic iridium complexes
  作者：Toshimichi Ohmura、Yasunori Yamamoto、Norio Miyaura

  DOI：10.1039/a802760i

  日期：——

  A cationic iridium complex, prepared via the hydrogenation of [Ir(cod)2]PF6–2PPr3 is found to be an excellent catalyst for the stereoselective isomerization of primary allyl silyl ethers to (E)-enol ethers and secondary allyl ethers to (Z)-enol ethers.

  一种阳离子铱配合物通过对[Ir(cod)2]PF6–2PPr3的氢化制备而成，发现其是初级烯丙基硅醚选择性异构化为(E)-烯醇醚和次级烯丙基醚异构化为(Z)-烯醇醚的优秀催化剂。