(6aR,11aS)-5,6,6a,11a-tetrahydronaphtho[1,2-b]benzofuran

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 萘并呋喃类
• 英文名称: (6aR,11aS)-5,6,6a,11a-tetrahydronaphtho[1,2-b]benzofuran
• 英文别名: (6aR,11aS)-5,6,6a,11a-tetrahydronaphtho[1,2-b][1]benzofuran
• 化学式: C₁₆H₁₄O
• 分子量: 222.287
• InChiKey: BGVSYDOVVPDSGO-GDBMZVCRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  1,2-二氢萘 、 1-乙酰氧基-2-碘苯 在 C₁₆H₁₆Cl₂N₂O₄Pd₂ 、 二环己胺 作用下， 以 N,N-二甲基乙酰胺 、 水 为溶剂， 反应 0.67h， 以42%的产率得到(6aR,11aS)-5,6,6a,11a-tetrahydronaphtho[1,2-b]benzofuran
  参考文献：
  名称：

  微波促进钯催化邻碘苯酚及其乙酸酯对二氢萘和铬烯的氧芳基化反应

  摘要：

  二氢萘 (1a)、两个富电子 (1b,c) 和一个缺电子 (2) 色烯与不同的邻碘苯酚及其乙酸酯 3a-h 的氧芳基化已经通过使用 Pd(OAc)2 (10 mol-%) 作为预催化剂和 Ag2CO3 作为碱在丙酮中作为溶剂或肟钯环 5 作为预催化剂和二环己胺作为碱在 DMA/H2O 中。当富电子色烯与被吸电子基团取代的邻碘苯酚在 Pd(OAc)2 和 Ag2CO3 存在下反应时，在微波加热下强烈加速的反应提供了最好的产率。然而，在贫电子色烯的情况下，富电子邻碘苯酚 3g 的产率最高。

  DOI：

  10.1002/ejoc.201100365

文献信息

• Enantioselective Oxy-Heck-Matsuda Arylations: Expeditious Synthesis of Dihydrobenzofuran Systems and Total Synthesis of the Neolignan (−)-Conocarpan
  作者：Allan R. Silva、Ellen C. Polo、Nelson C. Martins、Carlos Roque D. Correia

  DOI：10.1002/adsc.201701278

  日期：2018.1.17

  process is demonstrated by a concise total synthesis of the neolignan (−)‐conocarpan. X‐ray diffraction of an advanced brominated intermediate in the route to (−)‐conocarpan has allowed the unequivocal assignment of the absolute stereochemistry of the oxy‐Heck–Matsuda aryldihydrobenzofuran products. A rationale for the mechanism operating in these enantioselective oxy‐Heck–Matsuda reactions is also presented

  这项工作公开了使用多种苯乙烯烯烃生成手性二氢苯并呋喃的有效对映选择性氧-Heck-Matsuda反应的第一个实例。该反应以中等至良好的产率进行，具有高反式使用N，N-配体嘧啶-双恶唑啉（PyriBox）在90:10的对映选择性中具有非对映选择性（高达20：1）。oxy-Heck-Matsuda反应在温和的条件下和较低的催化剂载量下进行。新木脂素（-）-角果胶的简明全合成证明了该方法的可行性和实用性。在通往（-）-香柏树醇的途径中，对高级溴化中间体进行X射线衍射分析，使得对氧-赫克-松田芳基二氢苯并呋喃产品的绝对立体化学的明确分配成为可能。还介绍了在这些对映选择性氧-Heck-Matsuda反应中起作用的机理的基本原理。
• Palladium-catalyzed oxyarylation of olefins using silver carbonate as the base. Probing the mechanism by electrospray ionization mass spectrometry
  作者：Camilla D. Buarque、Vagner D. Pinho、Boniek Gontijo Vaz、Marcos N. Eberlin、Alcides J.M. da Silva、Paulo R.R. Costa

  DOI：10.1016/j.jorganchem.2010.05.014

  日期：2010.8

  (8 and 12) and electron-poor (10) olefins by ortho-iodophenols (3a–d) was studied using Ag2CO3 as the base, in acetone, and in the presence and absence of PPh3. The corresponding adducts of oxyarylation were obtained in moderate yields. The reaction mechanism was examined by electrospray ionization mass spectrometry (ESI-MS). Cationic arylpalladium intermediate (14), formed by the oxidative insertion

  以Ag 2 CO 3为碱，在丙酮中研究了邻碘苯酚（3a - d）的Pd（OAc）2催化富电子（8和12）和贫电子（10）烯烃的氧化芳基化。在有和没有PPh的情况下3。以中等收率获得了相应的氧化芳基加合物。通过电喷雾电离质谱法（ESI-MS）检查反应机理。通过将Pd（0）氧化插入3a形成的阳离子芳基钯中间体（14）和阳离子Palladacycles（15通过14与烯烃8和12的反应获得的）被ESI-MS截获并通过ESI-MS / MS进行表征。
• Palladium-catalyzed heteroannulation of cyclic alkenes by functionally substituted aryl iodides
  作者：Daniel E. Emrich、Richard C. Larock

  DOI：10.1016/j.jorganchem.2004.06.028

  日期：2004.11

  heteroannulation of cyclic and bicyclic alkenes by o-amino- and o-hydroxyaryl iodides. These processes are only successful with cyclic olefins in which the key alkylpalladium intermediate cannot undergo facile palladium β-hydride elimination. These reactions appear to involve: (1) oxidative addition of the aryl iodide to the palladium catalyst, (2) arylpalladation of the olefin, (3) possible coordination

  通过邻氨基-和邻羟基芳基碘化物的钯（0）催化的环状和双环烯烃的杂环化，以高收率生产二氢吲哚和2,3-二氢苯并呋喃。这些方法仅对其中关键烷基钯中间体不能进行便捷的氢化钯-氢化物消除的环状烯烃成功。这些反应似乎涉及：（1）芳基碘化物的氧化加成到钯催化剂上；（2）烯烃的芳基钯化；（3）内部亲核试剂与钯可能的配位；（4）六元形成Palladacycle，和（5）还原消除有机钯中间体，得到异环化产物并再生Pd（0）。
• Ligand-Free Palladium-Catalyzed Oxyarylation of Dihydronaphthal­enes and Chromenequinone with o-Iodophenols and 3-Iodolawsone in PEG-400: An Efficient Synthesis of 5-Carbapterocarpans and Pterocarpanquinones
  作者：Paulo Costa、Paula de Moraes、Francisco Gaspar、Rackel Borges、Chaquip Netto、Raquel Leão、Carmen Nájera

  DOI：10.1055/s-0034-1378745

  日期：——

  Dihydronaphthalenes were oxyarylated with o-iodophenols, in PEG-400 at 140 or 170 degrees C, leading regio-and stereoselectively to 5-carbapterocarpans. By using Pd(OAc)(2) (5-10 mol%) as precatalyst and Ag2CO3 (1.1 equiv) as base (conditions A), products were obtained in good to excellent chemical yields, in 5-30 minutes, irrespective of the pattern of substitution the starting materials. Alternatively, when p-hydroxyacetophenone oxime derived palladacycle (1 mol%) was used as precatalyst, and dicyclohexylamine (2 equiv) was used as base (silver-free, conditions B), the corresponding adducts were obtained in moderate to good yields, in 0.5 to 4 hours. Finally, the oxyarylation of dihydronaphthalenes and chromenquinone with o-iodophenols and 3-iodolawsone in PEG-400 under conditions A led regio-and stereoselectively to the formation of carbapterocarpanquinones and pterocarpanquinones in moderate yield.
• Pterocarpanquinones, aza-pterocarpanquinone and derivatives: Synthesis, antineoplasic activity on human malignant cell lines and antileishmanial activity on Leishmania amazonensis
  作者：Camilla D. Buarque、Gardenia C.G. Militão、Daisy J.B. Lima、Leticia V. Costa-Lotufo、Cláudia Pessoa、Manoel Odorico de Moraes、Edézio Ferreira Cunha-Junior、Eduardo Caio Torres-Santos、Chaquip D. Netto、Paulo R.R. Costa

  DOI：10.1016/j.bmc.2011.09.025

  日期：2011.11

  Pterocarpanquinones (1a-e) and the aza-pterocarpanquinone (2) were synthesized through palladium catalyzed oxyarylation and azaarylation of conjugate olefins, and showed antineoplasic effect on leukemic cell lines (K562 and HL-60) as well as colon cancer (HCT-8), gliobastoma (SF-295) and melanoma (MDA-MB435) cell lines. Some derivatives were prepared (3-8) and evaluated, allowing establishing the structural requirements for the antineoplasic activity in each series. Compound 1a showed the best selectivity index in special for leukemic cells while 2 showed to be more bioselective for HCT-8, SF-295 and MDA-MB435 cells. Pterocarpanquinones 1a and 1c-e, as well as 8 were the most active on amastigote form of Leishmania amazonensis in culture. Compounds 1a, 1c and 8 showed the best selectivity index. (C) 2011 Elsevier Ltd. All rights reserved.