3-phenyl-2-(trimethylsilyl)cyclobut-2-en-1-one | 216452-14-1

• 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-phenyl-2-(trimethylsilyl)cyclobut-2-en-1-one
• 英文别名: 3-Phenyl-2-trimethylsilylcyclobut-2-en-1-one
• CAS: 216452-14-1
• 化学式: C₁₃H₁₆OSi
• 分子量: 216.355
• InChiKey: KPOQJANTODDGEN-UHFFFAOYSA-N

物化性质

• 沸点：
  268.7±40.0 °C(predicted)
• 密度：
  1.02±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.29
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3-phenyl-2-(trimethylsilyl)cyclobut-2-en-1-one 以 苯 为溶剂， 反应 4.5h， 以37%的产率得到
  参考文献：
  名称：

  (Trialkylsilyl)vinylketenes:  Synthesis and Application as Diene Components in Diels−Alder Cycloadditions

  摘要：

  New strategies for the synthesis of (trialkylsilyl)vinylketenes ("TAS-vinylketenes") are described based on the photochemical Wolff rearrangement of alpha-silyl-alpha'-diazo-alpha,beta-unsaturated ketones and the 4 pi electrocyclic ring opening of cyclobutenones. These remarkably robust vinylketenes undergo highly regioselective [4 + 2] cycloadditions with reactive olefinic and acetylenic dienophiles to produce highly substituted cyclohexenones and phenols in which the ketene carbonyl dominates in controlling the regiochemical course of the reaction. The stereochemical course of these cycloadditions follows the Alder endo rule, as illustrated in the reaction of nitropropene with TBS-vinylketene 22.

  DOI：

  10.1021/jo981289u
• 作为产物：
  描述：

  4,4-Dichloro-3-phenyl-2-trimethylsilylcyclobut-2-en-1-one 在 四甲基乙二胺 、 溶剂黄146 、 锌 作用下， 以 乙醇 为溶剂， 以74%的产率得到3-phenyl-2-(trimethylsilyl)cyclobut-2-en-1-one
  参考文献：
  名称：

  (Trialkylsilyl)vinylketenes:  Synthesis and Application as Diene Components in Diels−Alder Cycloadditions

  摘要：

  New strategies for the synthesis of (trialkylsilyl)vinylketenes ("TAS-vinylketenes") are described based on the photochemical Wolff rearrangement of alpha-silyl-alpha'-diazo-alpha,beta-unsaturated ketones and the 4 pi electrocyclic ring opening of cyclobutenones. These remarkably robust vinylketenes undergo highly regioselective [4 + 2] cycloadditions with reactive olefinic and acetylenic dienophiles to produce highly substituted cyclohexenones and phenols in which the ketene carbonyl dominates in controlling the regiochemical course of the reaction. The stereochemical course of these cycloadditions follows the Alder endo rule, as illustrated in the reaction of nitropropene with TBS-vinylketene 22.

  DOI：

  10.1021/jo981289u

文献信息

• Rearrangement of an Intermediate Cyclopropyl Ketene in a Rh^II-Catalyzed Formal [4 + 1]-Cycloaddition Employing Vinyl Ketenes as 1,4-Dipoles and Donor–Acceptor Metallocarbenes
  作者：Kevin X. Rodriguez、Nicolai Kaltwasser、Tiffany A. Toni、Brandon L. Ashfeld

  DOI：10.1021/acs.orglett.7b00618

  日期：2017.5.19

  formal [4 + 1]-cycloaddition approach toward spirooxindole cyclopentenones is described. The diastereoselective cyclopropanation of vinyl ketenes with diazooxindoles as C1 synthons initiated a relatively mild formal [1,3]-migration of an intermediate cyclopropyl ketene to provide spirooxindoles in good to excellent yields (36–99%).

  描述了一种Rh II催化的螺环吲哚环戊烯酮的正式[4 +1]-环加成方法。乙烯基烯酮与重氮恶吲哚作为C1合成子的非对映选择性环丙烷化引发了中间体环丙基烯酮的相对温和的形式[1,3]迁移，从而以良好的产率（36％至99％）提供了螺硫醇。
• [4+3]-Cycloaddition Reaction of Sulfilimines with Cyclobutenones: Access to Benzazepinones
  作者：Xiaozhou Xie、Jiangtao Sun

  DOI：10.1021/acs.orglett.1c03413

  日期：2021.11.19

  A catalyst-free [4+3]-cycloaddition reaction of N-aryl sulfilimines with cyclobutenones is described, which provides a straightforward protocol for synthesizing 1,5-dihydro-2H-benzo[b]azepin-2-ones under mild reaction conditions. This reaction features a broad substrate scope and good functional group tolerance and does not require catalysts or additives. Moreover, using N-pyridinyl sulfilimine as

  描述了N-芳基硫亚胺与环丁烯酮的无催化剂 [4+3] -环加成反应，为在温和反应下合成 1,5-二氢-2 H-苯并 [ b ]azepin-2-ones提供了一个简单的方案状况。该反应具有广泛的底物范围和良好的官能团耐受性，并且不需要催化剂或添加剂。此外，以N-吡啶基硫亚胺为底物，还制备了一系列吡啶并氮杂酮类化合物。
• An unusual stereoretentive 1,3-quaternary carbon shift resulting in an enantioselective Rh^II-catalyzed formal [4+1]-cycloaddition between diazo compounds and vinyl ketenes
  作者：Kevin X. Rodriguez、Tara C. Pilato、Brandon L. Ashfeld

  DOI：10.1039/c8sc00020d

  日期：——

  Enantioselective quaternary carbon construction in the assembly of cyclopentenones employing a RhII-catalyzed, formal [4+1]-cycloaddition is described. A Rh2(S-TCPTTL)4-catalyzed cyclopropanation of a vinyl ketene with a disubstituted diazo compound initiates a stereoretentive, accelerated ring expansion to provide the cycloadduct in good to excellent yields and enantioselectivity.

  描述了采用 Rh II催化的正式 [4+1]-环加成反应组装环戊烯酮时的对映选择性季碳结构。Rh 2 ( S -TCPTTL) 4催化的乙烯基烯酮与二取代的重氮化合物的环丙烷化引发立构保留、加速环扩张，从而以良好至优异的产率和对映选择性提供环加合物。
• Generation of Functionalized Azepinone Derivatives via a (4 + 3)-Cycloaddition of Vinyl Ketenes and α-Imino Carbenes Derived from <i>N</i>-Sulfonyl-triazoles
  作者：Harrison M. Hill、Zachary D. Tucker、Kevin X. Rodriguez、Katelyn A. Wendt、Brandon L. Ashfeld

  DOI：10.1021/acs.joc.1c03002

  日期：2022.3.4

  3)-cycloaddition between vinyl ketenes and N-sulfonyl-1,2,3-triazoles for the construction of azepinone products is described. Employing vinyl ketenes as a 1,4-dipolar surrogate, instead of the more commonly used dienyl moieties, allows for the intermolecular and selective formation of azepinone products over a potential (3 + 2)-cycloadduct under mild reaction conditions allows for the generation of azepinone products

  描述了用于构建氮杂酮产品的乙烯基乙烯酮和N-磺酰基-1,2,3-三唑之间的分子间 Rh II催化的形式 (4 + 3) -环加成。使用乙烯基乙烯酮作为 1,4-偶极替代物，而不是更常用的二烯基部分，允许在温和的反应条件下通过潜在的 (3 + 2)-环加合物在分子间和选择性地形成氮杂酮产物，从而产生氮杂酮产物的收率高达 98%。
• Rational Design and Identification of Harmine‐Inspired, <i>N</i> ‐Heterocyclic DYRK1A Inhibitors Employing a Functional Genomic In Vivo <i>Drosophila</i> Model System**
  作者：Francisco J. Huizar、Harrison M. Hill、Emily P. Bacher、Kaitlyn E. Eckert、Eva M. Gulotty、Kevin X. Rodriguez、Zachary D. Tucker、Monimoy Banerjee、Haining Liu、Olaf Wiest、Jeremiah Zartman、Brandon L. Ashfeld

  DOI：10.1002/cmdc.202100512

  日期：2022.2.16

  dynamics simulations, and by employing a high-throughput functional genomics in vivo Drosophila model system that substantiated in vitro inhibition assays, new N-heterocyclic molecular scaffolds were discovered as effective inhibitors of the phosphotyrosine kinase DYRK1A. This study provides the framework for the future discovery of safe, effective small molecules to ameliorate DYRK1A overexpression phenotypes

  在分子动力学模拟的指导下，并通过采用证实体外抑制测定的高通量体内功能基因组学果蝇模型系统，发现新的N-杂环分子支架作为磷酸酪氨酸激酶DYRK1A的有效抑制剂。这项研究为未来发现安全、有效的小分子来改善 DYRK1A 过度表达表型提供了框架。