2-(triflyloxy)bicyclo[4.2.0]octa-1,3,5-triene-8-one | 1402160-76-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚满类
• 英文名称: 2-(triflyloxy)bicyclo[4.2.0]octa-1,3,5-triene-8-one
• 英文别名: 6-(triflyloxy)bicyclo[4.2.0]octa-1,3,5-trien-7-one；(8-Oxo-2-bicyclo[4.2.0]octa-1(6),2,4-trienyl) trifluoromethanesulfonate
• CAS: 1402160-76-2
• 化学式: C₉H₅F₃O₄S
• 分子量: 266.198
• InChiKey: NDTSJBPKAUJKJC-UHFFFAOYSA-N

物化性质

• 沸点：
  358.7±42.0 °C(Predicted)
• 密度：
  1.677±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  68.8
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2-(triflyloxy)bicyclo[4.2.0]octa-1,3,5-triene-8-one 在 甲醇 、 sodium tetrahydroborate 、 四(三苯基膦)钯 、 potassium carbonate 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 1.58h， 生成 5-Pyrimidin-5-ylbicyclo[4.2.0]octa-1(6),2,4-trien-7-ol
  参考文献：
  名称：

  [EN] MOLECULAR EDITING OF MULTIPLE C-H BONDS BY LEVERAGING RECOGNITION OF DISTANCE, GEOMETRY AND CHIRALITY
  [FR] ÉDITION MOLÉCULAIRE DE LIAISONS C-H MULTIPLES PAR EXPLOITATION DE LA RECONNAISSANCE DE LA DISTANCE, DE LA GÉOMÉTRIE ET DE LA CHIRALITÉ

  摘要：

  This disclosure provides functional templates that direct Pd to functionalize multiple C-H bonds in polycyclic aza-arenes such as quinolines and related heterocycles at locations that are difficult to isolate and reach for substitution. Herein disclosed are two conceptually distinct directing templates (T) that enable site- selective C6 and C7-H activation of polycyclic aza-arenes. These catalytic pyridine-based templates recruit the aza-arene substrate throughN-coordination, enabling the directing arm to deliver the catalyst and precisely activate remote and adjacent C6 or C7-H bond (Fig. 1d). In parallel, we discovered that the use of a simple and readily prepared template chaperone (TC) can turn over the directing template, allowing it to be used catalytically for the first time. Notably, chiral recognition is vital in the granular discrimination between competing C3 and C7-H bonds when the differentiation via distance and geometry is insufficient. Thus, precise recognition of a directing template's distance, geometry and chirality now enables the iterative C-H editing of quinoline and related pharmacophores at any desired site and order. The methods disclosed herein can also be used for diverse and late-stage modification of heterocycle-based drug molecules and pharmacophores.

  公开号：

  WO2023212565A2
• 作为产物：
  描述：

  8-(tert-butyldimethylsilyl)oxy-8-ethoxy-2-(triflyloxy)bicyclo[4.2.0]octa-1,3,5-triene 在 三氟化硼乙醚 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 2.0h， 以73%的产率得到2-(triflyloxy)bicyclo[4.2.0]octa-1,3,5-triene-8-one
  参考文献：
  名称：

  三氟乙氧基取代的苯并环丁烯酮，有机锂试剂和通过碳-碳键裂解形成的炔烃促进的亲油性物质的三组分偶联

  摘要：

  在亲核试剂的存在下，用有机锂试剂处理带有四氟环的四氟环附近的带有三氟乙氧基的苯并环丁烯酮，可以有效地得到三组分偶联的α-芳基酮。机理研究表明，通过苯并环丁烯氧化物中间体的碳-碳键裂解，芳烃的生成促进了反应，这促使我们从三氟乙氧基取代的苯并环丁烯酮甲硅烷基乙缩醛前体中找到氟化物介导的芳烃生成方法。

  DOI：

  10.1021/acs.orglett.7b00242

文献信息

• Rhodium(I)-Catalyzed Carboacylation/Aromatization Cascade Initiated by Regioselective C−C Activation of Benzocyclobutenones
  作者：Tianwen Sun、Yuna Zhang、Bo Qiu、Yafei Wang、Yuting Qin、Guangbin Dong、Tao Xu

  DOI：10.1002/anie.201713179

  日期：2018.3.5

  Described here is the first example of a rhodium‐catalyzed carboacylation/aromatization cascade of a C=O bond by C−C activation. In this transformation, a reactive rhodaindanone complex is regioselectively generated and adds across a C=O bond with subsequent elimination, thus providing a unique strategy to access a multisubstituted benzofuran scaffold. A diverse range of benzofuran analogues were obtained

  这里描述的是第一个通过CC活化的C = O键的铑催化的碳酰化/芳香化级联反应的第一个例子。在这种转化中，反应性的若丹丹酮络合物是区域选择性生成的，并通过一个C = O键加成并随后被消除，从而提供了一种独特的策略来接近多取代的苯并呋喃支架。以高收率获得了多种苯并呋喃类似物。机理研究表明，三环内酯是可行的中间体。将该方法应用于C13-deOH-乙烯基呋喃呋喃和C13-deOH-二氢吲哚酮G的全合成。
• 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。
• Synthesis of Diverse γ-Aryl-β-ketoesters via Aryne Intermediates Generated by C–C Bond Cleavage
  作者：Keisuke Uchida、Yasunori Minami、Suguru Yoshida、Takamitsu Hosoya

  DOI：10.1021/acs.orglett.9b03418

  日期：2019.11.15

  γ-aryl-β-ketoesters through γ-aryl-β-ketoester-type arynes triggered by C–C bond cleavage has been developed. The Mukaiyama aldol reaction of 6-(triflyloxy)benzocyclobutenones with ketene silyl acetals and subsequent treatment of resulting 6-(triflyloxy)benzocyclobutenols with a base triggered the efficient generation of γ-aryl-β-ketoester-type arynes, which reacted with various arynophiles to provide

  已经开发了一种通过C–C键断裂引发的γ-芳基-β-酮酸酯型芳烃合成各种γ-芳基-β-酮酸酯的方法。6-（三氟乙氧基）苯并环丁烯酮与乙烯酮甲硅烷基乙缩醛的Mukaiyama羟醛反应和随后用碱处理所得的6-（三氟乙氧基）苯并环丁烯醇引发了γ-芳基-β-酮酸酯型芳烃的有效生成，该芳烃与各种嗜酸粒菌反应提供广泛的γ-芳基-β-酮酸酯。通过ALK抑制剂类似物的合成证明了该方法的合成效用。
• Rhodium-Catalyzed Regioselective Carboacylation of Olefins: A CC Bond Activation Approach for Accessing Fused-Ring Systems
  作者：Tao Xu、Guangbin Dong

  DOI：10.1002/anie.201202771

  日期：2012.7.23

  Cut and sew: A rhodium‐catalyzed regioselective carboacylation reaction of benzocyclobutenones was developed (see scheme). Directed by the pendant olefins, the C1C2 bond is selectively cleaved rather than the C1C8 bond. Subsequent alkene insertion leads to complex fused‐ring systems. This reaction provides facile access to natural‐product‐like polycyclic structures in a chemoselective and atom‐economic

  切割和缝制：开发了铑催化的苯并环丁烯酮的区域选择性碳酰化反应（参见方案）。在侧链烯烃的引导下，C1C2键被选择性裂解，而不是C1C8键。随后的烯烃插入导致复杂的稠环系统。该反应以化学选择性和原子经济的方式提供了对类似于天然产物的多环结构的便捷访问。