(3-((2-methylallyl)oxy)prop-1-yn-1-yl)benzene | 57187-82-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (3-((2-methylallyl)oxy)prop-1-yn-1-yl)benzene
• 英文别名: 3-[(2-methyl-2-propenyl)oxy]-1-phenyl-1-propyne；Benzene, [3-[(2-methyl-2-propenyl)oxy]-1-propynyl]-；3-(2-methylprop-2-enoxy)prop-1-ynylbenzene
• CAS: 57187-82-3
• 化学式: C₁₃H₁₄O
• 分子量: 186.254
• InChiKey: OCJKBBZTQDKYFM-UHFFFAOYSA-N

物化性质

• 沸点：
  120-122 °C(Press: 0.9 Torr)
• 密度：
  0.98±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.23
• 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：

  (3-((2-methylallyl)oxy)prop-1-yn-1-yl)benzene 在 bis(cyclopentadienyl)bis(trimethylphosphane)titanium(II) 、 copper(II) sulfate 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 52.0h， 生成 2-phenyl-5-methyl-7-oxabicyclo<3.3.0>oct-1-en-3-one
  参考文献：
  名称：

  Development of a Titanocene-Catalyzed Enyne Cyclization/Isocyanide Insertion Reaction

  摘要：

  The first early transition metal-catalyzed enyne cyclization reaction is described. The system converts enyne substrates to bicyclic iminocyclopentenes through the use of 10 mol % of Cp(2)Ti(PMe(3))(2) in the presence of a silyl cyanide. Subsequent hydrolysis produces the corresponding bicyclic cyclopentenones in good overall yield. The cyclization reaction is tolerant of polar functional groups such as ethers, amines, and esters and is diastereoselective with certain chiral enyne substrates.

  DOI：

  10.1021/ja00098a020
• 作为产物：
  描述：

  3-苯基-2-丙炔-1-醇 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 以98 %的产率得到(3-((2-methylallyl)oxy)prop-1-yn-1-yl)benzene
  参考文献：
  名称：

  Monoallenylidene Pd(II) 催化剂介导的两种不同的烯炔环异构化路线

  摘要：

  探索了以炔基三唑盐为亚丙基源开发的四种单亚丙基双膦Pd(II)催化剂在1,6-烯炔环异构化反应中的催化应用。使用复杂的 TAA(Et 3 P) 2 -PdCl·BF 4 – 3b或 TAA(Ph 3 P)开发了两种不同的反应途径，包括新型分子内桤木烯 (IMAE) 途径和常规环异构化途径2 -PdCl·BF 4 – 3c作为催化剂前驱体。

  DOI：

  10.1021/acs.orglett.2c03205

文献信息

• CO-Transfer Carbonylation Reactions. A Catalytic Pauson−Khand-Type Reaction of Enynes with Aldehydes as a Source of Carbon Monoxide
  作者：Tsumoru Morimoto、Koji Fuji、Ken Tsutsumi、Kiyomi Kakiuchi

  DOI：10.1021/ja0126881

  日期：2002.4.1

  The reaction of enynes with aldehydes in the presence of a catalytic amount of [RhCl(cod)](2)/dppp results in the Pauson-Khand-type reaction without the use of gaseous carbon monoxide to give bicyclic cyclopentenones in high yields (14 examples). Aldehydes serve as a source of carbon monoxide, and their carbonyl moiety is transferred to enynes, resulting in the formation of the carbonylated products

  在催化量的 [RhCl(cod)](2)/dppp 存在下，烯炔与醛的反应会导致 Pauson-Khand 型反应，而无需使用气态一氧化碳，以高产率得到双环环戊烯酮 (14例子）。醛作为一氧化碳的来源，它们的羰基部分被转移到烯炔，导致形成羰基化产物。该反应代表了 CO 转移羰基化的第一个例子。
• Rhodium-Catalyzed Pauson-Khand-Type Reaction Using Alcohol as a Source of Carbon Monoxide
  作者：Ji Hoon Park、Yoonhee Cho、Young Keun Chung

  DOI：10.1002/anie.201001246

  日期：2010.7.12

  cyclopentenones have been synthesized from enynes in alcohol in the presence of a rhodium catalyst through a newly developed auto‐tandem catalytic reaction. This process combines three mechanistically distinctive reactions—an oxidation of alcohols, a decarbonylation of aldehydes, and a carbonylative [2+2+1] cycloaddition (see scheme; dppp=propane‐l,3‐diylbis(diphenylphosphane)).

  三合一锅！双环环戊烯酮是在铑催化剂存在下，通过新开发的自动串联催化反应，由炔烃在醇中合成的。此过程结合了三个机械上独特的反应-醇的氧化，醛的脱羰基和羰基化的[2 + 2 + 1]环加成反应（请参见方案； dppp =丙烷-1,3-二联双（二苯基膦））。
• Rhodium-BisbenzodioxanPhos Complex-Catalyzed Homogeneous Enantioselective Pauson-Khand-Type Cyclization in Alcoholic Solvents
  作者：Fuk Yee Kwong、Hang Wai Lee、Liqin Qiu、Wai Har Lam、Yue-Ming Li、Hoi Lun Kwong、Albert S. C. Chan

  DOI：10.1002/adsc.200505105

  日期：2005.11

  s was found to be highly effective in the co-operative processeses of aldehyde decarbonylation and cascaded enantioselective Pauson–Khand-type reactions. Various 1,6-enynes were transformed to the corresponding bicyclic cyclopentenones in good yields and enantiomeric excesses (up to 96% ee). The attractive feature of this new Rh-catalyzed homogeneous dual catalysis system is that the reaction can be

  发现手性阻转异构二膦配体（S）-双苯并二恶烷膦在醛脱羰和级联对映选择性Pauson-Khand型反应的合作过程中非常有效。各种1,6-烯炔以良好的收率和对映体过量（最高ee为96％）转化为相应的双环环戊烯酮。这种新的Rh催化均相双重催化系统的吸引人之处在于该反应可以在酒精溶液中进行。
• Rhodium-Catalyzed Asymmetric Aqueous Pauson-Khand-Type Reaction
  作者：Fuk Yee Kwong、Yue Ming Li、Wai Har Lam、Liqin Qiu、Hang Wai Lee、Chi Hung Yeung、Kin Shing Chan、Albert S. C. Chan

  DOI：10.1002/chem.200401237

  日期：2005.6.20

  operationally simple protocol allows both catalyst and reactants to be handled under air without precautions. Various enynes were transformed to the corresponding bicyclic cyclopentenones in good yield and enantiomeric excess (up to 95 % ee). A study of the electronic effects of the enyne substrates revealed a correlation between the electronic properties of the substrates and the ee value obtained in

  开发了一种有趣的铑催化的不对称含水Pauson-Khand型反应。发现手性阻转异构体二吡啶基二膦配体在该系统中是高度有效的。该操作简单的方案允许催化剂和反应物都在空气中进行处理而无需采取预防措施。将各种烯炔以良好的收率和对映体过量（至多95％ee）转化为相应的双环环戊烯酮。对烯炔底物的电子效应的研究表明，底物的电子性质与Pauson-Khand型反应产物中获得的ee值之间存在相关性。从Hammett研究中观察到线性自由能关系。
• Iron-Mediated Radical Nitrohalogenation Reactions of Enynes with tert-Butyl Nitrite
  作者：Yingming Ren、Yaxin Ge、Qinqin Yan、Yunfei Tian、Zejiang Li、Jilai Wu、Yujie Yang、Lijun Li

  DOI：10.1055/a-1520-2192

  日期：2021.7

  A radical nitrohalogenation/cyclization of various enynes with tert-butyl nitrite has been developed that conveniently introduces useful nitro and halo groups into organic compounds. Some control experiments were performed to elucidate the mechanism. Further functional transformations proceeded well in this reaction system.

  已经开发出各种烯炔与亚硝酸叔丁酯的自由基硝基卤化/环化，可以方便地将有用的硝基和卤素基团引入有机化合物中。进行了一些对照实验以阐明机制。进一步的功能转化在该反应体系中进行得很好。