3,5-dimethoxybicyclo[4.2.0]octa-1(6),2,4-trien-7-one | 118112-18-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 3,5-dimethoxybicyclo[4.2.0]octa-1(6),2,4-trien-7-one
• 英文别名: 4,6-dimethoxybenzocyclobutenone；3,5-Dimethoxybicyclo[4.2.0]octa-1,3,5-trien-7-one
• CAS: 118112-18-8
• 化学式: C₁₀H₁₀O₃
• 分子量: 178.188
• InChiKey: ZKJZNVPLZBONJR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3,5-dimethoxybicyclo[4.2.0]octa-1(6),2,4-trien-7-one 在 potassium permanganate 、 sodium periodate 、 四氧化锇 、 lithium aluminium tetrahydride 、 potassium tert-butylate 、 水 、 三溴化硼 、 三乙胺 、 三氟乙酸酐 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 丙酮 为溶剂， 反应 50.0h， 生成 4,7,9-trimethoxy-1-(4-methoxyphenyl)-6H-anthra[1,9-bc]furan-6-one
  参考文献：
  名称：

  Total synthesis of penta-Me amurensin H and diptoindonesin G featuring a Rh-catalyzed carboacylation/aromatization cascade enabled by C C activation

  摘要：

  Oligostilbenoids represented a family of natural products, which contained one or several multifused benzofuran substructures and displayed promising biological activities towards cancer as well as immunological therapeutic targets. A convergent-divergent strategy featuring Rh-catalyzed carboacylation/aromatization cascade reaction based on C-C activation of benzocyclbutenones had been conceived. penta-Methyl amurensin H and diptoindolnesin G were successfully synthesized without any protecting groups, constituting a new entry towards oligostilbenoids' natural product synthesis. The synthesis completed within 10 steps for both natural products, suggesting conciseness and efficacy of the C-C activation in complex natural product synthesis. (C) 2019 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2019.02.040
• 作为产物：
  描述：

  在 盐酸 作用下， 反应 20.0h， 生成 3,5-dimethoxybicyclo[4.2.0]octa-1(6),2,4-trien-7-one
  参考文献：
  名称：

  Synthesis of substituted benzocyclobutenediones

  摘要：

  DOI：

  10.1021/jo00267a037

文献信息

• Site‐Selective C–C Cleavage of Benzocyclobutenones Enabled by a Blocking Strategy Using Nickel Catalysis
  作者：Jing‐Hong Guo、Yu Liu、Xin‐Cheng Lin、Tian‐Mu Tang、Bi‐Qin Wang、Ping Hu、Ke‐Qing Zhao、Feijie Song、Zhang‐Jie Shi

  DOI：10.1002/anie.202106709

  日期：2021.8.23

  Controlling the chemo- and regioselectivity of transition-metal-catalyzed C−C activation remains a great challenge. The transformations of benzocyclobutenones (BCBs) usually involve the cleavage of C1−C2 bond. In this work, an unprecedented highly selective cleavage of C1−C8 bond with the insertion of alkynes is achieved by using blocking strategy via Ni catalysis, providing an efficient method for

  控制过渡金属催化的 C-C 活化的化学和区域选择性仍然是一个巨大的挑战。苯并环丁烯酮 (BCB) 的转化通常涉及 C1-C2 键的断裂。在这项工作中，通过 Ni 催化使用封闭策略实现了前所未有的 C1-C8 键的高选择性裂解和炔烃的插入，为合成 1,8-二取代萘提供了一种有效的方法。值得注意的是，转化后可以很容易地去除封闭基团。
• Tandem Nickel-Catalyzed Dimerization/(4+2) Cycloaddition of Terminal Alkynes with Four-Membered Ring Ketones
  作者：Christophe Aïssa、Manuel Barday、Eva Nicolas、Bradley Higginson、François Delmotte、Martin Appelmans

  DOI：10.1055/a-1671-8497

  日期：2022.2

  Controlling the behavior of terminal alkynes in metal-catalyzed intermolecular tandem reactions is a formidable challenge despite the potential advantage offered by these strategies in modern synthesis. Herein, we describe that a nickel catalyst enables a tandem process involving the rapid dimerization of terminal alkynes into 1,3-enynes and the cycloaddition of these intermediates with an azetidinone

  尽管这些策略在现代合成中具有潜在优势，但在金属催化的分子间串联反应中控制末端炔烃的行为是一项艰巨的挑战。在此，我们描述了镍催化剂能够实现串联过程，该过程涉及末端炔烃快速二聚为 1,3-烯炔，以及这些中间体与氮杂环丁酮、氧杂环丁酮或苯并环丁烯酮的环加成反应。重要的是，不需要缓慢或连续添加试剂和催化剂来协调它们的反应性。这些结果与之前带有应变四元环底物的末端炔烃的环加成形成鲜明对比，后者导致低聚或环三聚，但叔丁基乙炔除外。
• Thermal <i>Hetero</i>-Diels–Alder Reaction of Benzocyclobutenones with Isatins To Form 2-Oxindole Spirolactones
  作者：Thomas Wurm、Ben W. H. Turnbull、Brett R. Ambler、Michael J. Krische

  DOI：10.1021/acs.joc.7b02769

  日期：2017.12.15

  or “ortho-quinoid ketene methides”, which engage in intermolecular [4+2] cycloadditions with isatins 2a–2f to form 2-oxindole spirolactones 3a–3l. This process tolerates an array of different functional groups and substitution patterns, and is applicable to unprotected isatins 2b–2f bearing free NH-functionalities. The superior performance of isatins compared to other carbonyl based dienophiles was

  苯并环丁烯酮1a – 1g在间二甲苯溶剂中于 150 °C 下发生环化，形成瞬态 α-氧代-邻醌二甲烷或“邻醌烯酮甲基化物”，其与靛红2a – 2f进行分子间 [4+2] 环加成，生成形成 2-羟吲哚螺内酯3a – 3l 。该过程可耐受一系列不同的官能团和取代模式，并且适用于带有游离 NH 官能团的未受保护的靛红2b – 2f 。与其他基于羰基的亲二烯体相比，靛红的优越性能通过量子化学计算得到了证明和合理化。
• Pd/C-Catalyzed Stereoselective Arene Hydrogenation of Benzocyclobutenes Enabled by π-Bond Localization
  作者：Zhan Shi、Licheng Lu、Ping Lu

  DOI：10.1021/acs.orglett.4c01737

  日期：2024.6.28

  We developed here a Pd/C-catalyzed diastereoselective cis-hydrogenation of benzocyclobutene derivatives under mild conditions to deliver an array of bicyclo[4.2.0]octane scaffolds with up to five stereocenters. The π-bond localization enabled hydrogenation of the arene moiety to occur even at room temperature under 1 atm of a H2 atmosphere.

  我们在这里开发了一种 Pd/C 催化的苯并环丁烯衍生物在温和条件下的非对映选择性顺式氢化，以提供一系列具有多达五个立构中心的双环[4.2.0]辛烷支架。 π键定位使得芳烃部分的氢化即使在室温下1atm的H 2气氛下也能发生。
• Rapid, convergent, and regioselective synthesis of anthracenes
  作者：John J. Fitzgerald、Neville E. Drysdale、R. A. Olofson

  DOI：10.1021/jo00052a027

  日期：1992.12

  Anthracenes are obtained in moderate to good yield by the simultaneous treatment of benzocyclobutenols and halobenzenes with LTMP in tetrahydropyran. In the key step of this one-pot process, o-toluoyl anion intermediates from the known ring-opening of benzocyclobutenoxides add to halobenzene derived arynes. Methoxy-substituted benzocyclobutenols which are readily made regiospecifically by known methods also react regiospecifically with the single benzyne generated from either a 2- or 3-haloanisole. For example, the only trimethoxyanthracene isolated (48% yield) from the reaction of 6-methoxybenzocyclobutenol (8) with 5-chloro-1,3-dimethoxybenzene is the 1,3,8-isomer 20. When 1,2-dihydrocyclobuta[l]phenanthren-1-ol (14) and/or halonaphthalenes are the reactants, benzannulated anthracenes are formed; e.g., tribenz[a,c,h]anthracene in 68% yield from 14 and bromonaphthalene. In another extension, pentaphene (31) was made in one pot from o-dichlorobenzene.