4-oxo-6-(trimethylsilyl)-5-hexynoic acid | 187085-79-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: 4-oxo-6-(trimethylsilyl)-5-hexynoic acid
• 英文别名: 4-oxo-6-(trimethylsilyl)hex-5-ynoic acid；4-Oxo-6-trimethylsilylhex-5-ynoic acid
• CAS: 187085-79-6
• 化学式: C₉H₁₄O₃Si
• 分子量: 198.294
• InChiKey: MYDKOOSBGMKPCE-UHFFFAOYSA-N

物化性质

• 熔点：
  59-64 °C
• 沸点：
  285.5±23.0 °C(Predicted)
• 密度：
  1.055±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  54.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-oxo-6-(trimethylsilyl)-5-hexynoic acid 在 N-甲基吗啉 、 2-氯-4,6-二甲氧基-1,3,5-三嗪 、 lithium iodide 作用下， 以 乙酸乙酯 为溶剂， 反应 24.0h， 生成 2-[Benzyl-(4-oxo-6-trimethylsilanyl-hex-5-ynoyl)-amino]-propionic acid
  参考文献：
  名称：

  New Approach for the General Synthesis of Oxotetrahydroindoles via Intramolecular Cycloadditions of Azomethine Ylides with Tethered Alkynes

  摘要：

  A new method for the synthesis of oxotetrahydroindoles has been achieved employing an intramolecular dipolar cycloaddition approach involving mesoionic species (munchnones) with electron-deficient alkynes. The methodology is quite general and convergent as shown by the synthesis of a variety of tri- and tetrasubstituted oxotetrahydroindoles 18, 21, 24, 27, 30, and 34. LiI-based ester cleavage in the presence of an electrophilic acetylenic ketone was critical for formation of the requisite cycloaddition substrates. The cycloaddition is virtually unaffected by the presence of gem-dimethyl groups in the side chain (cf. 38). The presence of a substituted benzyl or a phenethyl moiety on nitrogen, a polarized acetylene, and an appropriate tether between dipole and dipolarophile are essential for obtaining optimal efficiency.

  DOI：

  10.1021/jo9614598
• 作为产物：
  描述：

  6-三甲基甲硅烷基己-5-炔酸 在 dirhodium(II) tetrakis(caprolactam) 叔丁基过氧化氢 作用下， 以 水 为溶剂， 反应 15.0h， 以70%的产率得到4-oxo-6-(trimethylsilyl)-5-hexynoic acid
  参考文献：
  名称：

  己内酯二甲酸在水中催化的炔丙基氧化：有效获得α，β-乙炔酮

  摘要：

  己酸内酯（II）（1，Rh 2（cap）4）与70％w / w叔丁基过氧化氢水溶液（T-HYDRO）是一种高效的催化氧化方案，用于将炔烃进行CH选择性氧化成炔丙基酮。在温和条件下，使用廉价且易于处理的氧化剂，很容易在水性溶剂中发生氧化。以高达80％的分离产率生成α，β-乙炔羰基化合物。

  DOI：

  10.1021/jo800382p

文献信息

• Asymmetric reduction of ethynyl ketones and ethynylketoesters by secondary alcohol dehydrogenase from Thermoanaerobacter ethanolicus †
  作者：Christian Heiss、Robert S. Phillips

  DOI：10.1039/b001329n

  日期：——

  Secondary alcohol dehydrogenase (SADH) from Thermoanaerobacter ethanolicus, an NADP-dependent, thermostable oxidoreductase, reduces ethynyl ketones and ethynylketoesters enantioselectively to the corresponding propargyl (propargyl = prop-2-ynyl) alcohols. Ethynyl ketones, in general, are reduced with moderate enantioselectivity (with the exception of 4-methylpent-1-yn-3-one, which gives the (S)-alcohol

  仲醇脱氢酶（SADH）从嗜热ethanolicus，一个北美发展计划依赖性的热稳定氧化还原酶将乙炔基酮和乙炔基酮酸酯对映选择性地还原为相应的炔丙基（炔丙基=炔-2-炔基） 酒类。乙炔基酮类通常以中等对映选择性降低（除 4-甲基戊-1-yn-3-一，得到（S）醇的ee> 98％）。虽然乙炔基酮类带有少量（最多正丙基）烷基取代基还原为（S）醇，较大的乙炔基酮类给出（R）-醇。相反，乙炔基酮酸酯被转化为具有优异光学纯度的（R）-乙炔基羟基酯。出乎意料的是，与乙炔基羟基酯相比，异丙基乙炔基酮酯具有更高的化学收率和更高的对映选择性。甲基或乙基乙炔基酮酸酯。光学纯的乙炔基羟基酯可用作不对称合成的有用的手性结构单元。
• 2-Acyl-1-aryl-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazole derivatives: Versatile fluorescent probes with remarkably large Stokes shift
  作者：Nejc Petek、Bibi Erjavec、Dejan Slapšak、Aljaž Gaber、Uroš Grošelj、Franc Požgan、Sebastijan Ričko、Bogdan Štefane、Marina Klemenčič、Jurij Svete

  DOI：10.1016/j.dyepig.2022.110224

  日期：2022.5

  A series of thirteen 2-acyl-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazole derivatives were synthesized by using a copper-catalyzed azomethine-imine-alkyne cycloaddition as a key step. These bimane-related fluorescent compounds with λex = 338–400 nm and λem = 522–644 nm exhibit interesting and promising optical properties, including a remarkably large Stokes shift (150–268 nm), positive solvatochromism

  以铜催化偶氮甲亚胺-炔烃环加成为关键步骤，合成了13种2-酰基-6,7-二氢-1H , 5H-吡唑并[1,2 - a ]吡唑衍生物。这些具有 λ ex  = 338-400 nm 和 λ em = 522-644 nm的双烷相关荧光化合物 表现出有趣且有前途的光学特性，包括非常大的斯托克斯位移 (150-268 nm)、正溶剂化显色性和强烈的发射依赖性在 pH 2-10 范围内对 pH 的强度。苯并三唑啉和N-琥珀酰亚胺酯官能化化合物成功地用作蛋白质标记的荧光探针。
• CONUGATED PROTEINS AND PEPTIDES
  申请人：Godwin Antony Robert

  公开号：US20120014905A1

  公开（公告）日：2012-01-19

  Novel compounds of the general formula (I): in which X represents a polymer; Q represents a linking group; W represents an electron-withdrawing moiety or a moiety preparable by reduction of an electron-withdrawing moiety; each of R 1 and R 2 independently represents a hydrogen atom or a C 1-4 alkyl group; and either Z 1 represents a protein or a peptide linked to CR 2 via a nucleophilic moiety, and Z 2 represents a molecule linked to CR 2 via a nucleophilic moiety, or Z 1 and Z 2 together represent a single group derived from a protein or peptide linked to CR via two nucleophilic moieties.

  通式（I）的新化合物：其中X代表聚合物；Q代表连接基团；W代表一个电子吸引基团或通过还原电子吸引基团制备的基团；R1和R2各自独立地代表氢原子或C1-4烷基基团；Z1代表通过亲核基团与CR2链接的蛋白质或肽，Z2代表通过亲核基团与CR2链接的分子，或者Z1和Z2一起代表由蛋白质或肽派生出的单个基团，通过两个亲核基团与CR链接。
• New Approach for the General Synthesis of Oxotetrahydroindoles via Intramolecular Cycloadditions of Azomethine Ylides with Tethered Alkynes
  作者：Naresh K. Nayyar、Darrell R. Hutchison、Michael J. Martinelli

  DOI：10.1021/jo9614598

  日期：1997.2.1

  A new method for the synthesis of oxotetrahydroindoles has been achieved employing an intramolecular dipolar cycloaddition approach involving mesoionic species (munchnones) with electron-deficient alkynes. The methodology is quite general and convergent as shown by the synthesis of a variety of tri- and tetrasubstituted oxotetrahydroindoles 18, 21, 24, 27, 30, and 34. LiI-based ester cleavage in the presence of an electrophilic acetylenic ketone was critical for formation of the requisite cycloaddition substrates. The cycloaddition is virtually unaffected by the presence of gem-dimethyl groups in the side chain (cf. 38). The presence of a substituted benzyl or a phenethyl moiety on nitrogen, a polarized acetylene, and an appropriate tether between dipole and dipolarophile are essential for obtaining optimal efficiency.
• Propargylic Oxidations Catalyzed by Dirhodium Caprolactamate in Water: Efficient Access to α,β-Acetylenic Ketones
  作者：Emily C. McLaughlin、Michael P. Doyle

  DOI：10.1021/jo800382p

  日期：2008.6.1

  hydroperoxide (T-HYDRO) is a highly effective catalytic oxidation protocol for the selective C−H oxidation of alkynes to propargylic ketones. The oxidation occurs readily in aqueous solvent under mild conditions with an inexpensive and easily handled oxidant. α,β-Acetylenic carbonyl compounds are formed in up to 80% isolated yield.

  己酸内酯（II）（1，Rh 2（cap）4）与70％w / w叔丁基过氧化氢水溶液（T-HYDRO）是一种高效的催化氧化方案，用于将炔烃进行CH选择性氧化成炔丙基酮。在温和条件下，使用廉价且易于处理的氧化剂，很容易在水性溶剂中发生氧化。以高达80％的分离产率生成α，β-乙炔羰基化合物。