10-methyl-2-phenylphenanthrene | 1146542-62-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 10-methyl-2-phenylphenanthrene
• 英文别名: 10-Methyl-2-phenylphenanthrene
• CAS: 1146542-62-2
• 化学式: C₂₁H₁₆
• 分子量: 268.358
• InChiKey: UYFOLAWQVTXSSE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  21
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  4'-bromo-[1,1'-biphenyl]-2-carbaldehyde 在 sodium tetrahydroborate 、 copper(l) iodide 、 四(三苯基膦)钯 、 四溴化碳 、 [(C₆F₅)₃PAuNTf₂] 、 四丁基碘化铵 、 potassium carbonate 、 双三氟甲烷磺酰亚胺 、 三苯基膦 作用下， 以 四氢呋喃 、 甲醇 、 水 、 乙腈 为溶剂， 反应 5.0h， 生成 10-methyl-2-phenylphenanthrene
  参考文献：
  名称：

  黄金催化的6-Exo-Dig环异构化：一种多功能的官能化菲的方法

  摘要：

  已经开发了一种新型的金催化的邻炔丙基联芳基的6- exo - dig环异构化方法，该方法可以方便地获得官能化的菲，而且收率大体上很高。该方法的显着特征是易于获得的起始原料，温和的反应条件和广泛的底物范围。

  DOI：

  10.1002/asia.201400034

文献信息

• Oxidative, Iodoarene‐Catalyzed Intramolecular Alkene Arylation for the Synthesis of Polycyclic Aromatic Hydrocarbons
  作者：Zhensheng Zhao、Liam H. Britt、Graham K. Murphy

  DOI：10.1002/chem.201804786

  日期：2018.11.16

  metal‐free and chemoselective oxidative intramolecular coupling of arene and alkene C−H bonds is reported. The active hypervalent iodine (HVI) reagent, generated catalytically in situ from iodotoluene and meta‐chloroperoxybenzoic acid (m‐CPBA), reacts with o‐vinylbiphenyls to generate polyaromatic hydrocarbons in up to 95 % yield. Experimental evidence suggests the reactions proceed though vinyliodonium

  据报道，芳烃和烯烃CH键具有催化，无金属和化学选择性的氧化分子内偶联作用。由碘代甲苯和间氯过氧苯甲酸（m- CPBA）原位催化生成的活性高价碘（HVI）试剂与邻乙烯基联苯反应生成多芳烃，产率高达95％。实验证据表明，反应是通过乙烯基碘鎓和（可能的）亚乙烯基phen中间体进行的。
• Triflic acid promoted synthesis of polycyclic aromatic compounds
  作者：Ang Li、Daniel J. DeSchepper、Douglas A. Klumpp

  DOI：10.1016/j.tetlet.2009.02.042

  日期：2009.4

  The triflic acid (CF3SO3H) promoted cyclizations of 2-styrylbiaryls are found to be useful for the synthesis of polycyclic aromatic compounds, including functionalized derivatives of polycyclic aromatic compounds and heterocyclic systems. The reaction involves cationic cyclization followed by an elimination of benzene from the intermediate product.

  发现三氟甲磺酸（CF 3 SO 3 H）促进的2-苯乙烯基联芳基的环化可用于合成多环芳族化合物，包括多环芳族化合物的官能化衍生物和杂环体系。该反应涉及阳离子环化，然后从中间产物中消除苯。
• Hypervalent iodine-mediated oxidative alkene arylation: a thorough analysis
  作者：Liam H. Britt、Zhensheng Zhao、Graham K. Murphy

  DOI：10.1139/cjc-2022-0032

  日期：2022.8.1

  A hypervalent iodine (HVI)-mediated, oxidative alkene arylation reaction has been developed. Both Koser’s reagent (PhI(OH)OTs) and (diacetoxyiodo)toluene (TolI(OAc)₂) were equally viable as oxidants, which reacted with ortho-vinylbiphenyl derivatives to produce tri-, tetra-, and pentacyclic polycyclic aromatic hydrocarbons in yields up to 97%. Comparison of this stoichiometric reaction with a previously reported catalytic process showed that these protocols were largely complementary, and that they likely operate via the same general mechanistic sequence involving vinyliodonium salts decomposing into vinylene phenonium ions. Various mechanistic control experiments were conducted, which ruled out epoxides as intermediates, and which showed that E- and Z-alkene geometry in 10-substituted ortho-vinylbiphenyls had no impact on the ensuing isomeric product distributions. These experiments strongly supported the formation of E-vinyliodonium ions as initial reaction intermediates, and while the occurrence of 1,2-phenyl shift products was a common phenomenon, we concluded that alkyl substitution on the ortho-vinylbiphenyl was a requirement for this alternate pathway to occur.

  我们开发了一种以高价碘 (HVI) 为介质的氧化烯芳基化反应。Koser 试剂（PhI(OH)OTs）和（二乙酰氧基碘）甲苯（TolI(OAc)2）同样可用作氧化剂，它们与正乙烯基联苯衍生物反应生成三环、四环和五环多环芳烃，收率高达 97%。将这一化学反应与之前报道的催化过程进行比较后发现，这两种方法在很大程度上是互补的，它们很可能通过相同的机理顺序进行操作，即乙烯基碘鎓盐分解成乙烯基鎓离子。我们进行了各种机理控制实验，排除了环氧化物作为中间体的可能性，实验结果表明，10-取代正乙烯基联苯中的 E-和 Z-烯几何形状对随后的异构产物分布没有影响。这些实验有力地支持了 E-乙烯基碘离子作为初始反应中间体的形成，虽然 1,2-苯基转变产物的出现是一个普遍现象，但我们得出结论，正乙烯基联苯上的烷基取代是发生这种替代途径的必要条件。
• Gold-Catalyzed 6-<i>Exo</i>-<i>Dig</i>Cycloisomerization: A Versatile Approach to Functionalized Phenanthrenes
  作者：Chao Shu、Long Li、Cheng-Bin Chen、Hong-Cheng Shen、Long-Wu Ye

  DOI：10.1002/asia.201400034

  日期：2014.6

  A novel gold‐catalyzed 6‐exo‐dig cycloisomerization of o‐propargylbiaryls has been developed that provides ready access to functionalized phenanthrenes in largely good to excellent yields. Notable features of this method are readily available starting materials, mild reaction conditions, and broad substrate scope.

  已经开发了一种新型的金催化的邻炔丙基联芳基的6- exo - dig环异构化方法，该方法可以方便地获得官能化的菲，而且收率大体上很高。该方法的显着特征是易于获得的起始原料，温和的反应条件和广泛的底物范围。