3-Phenyl-2-triethylsilylcyclobut-2-en-1-one | 216452-15-2

• 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-triethylsilylcyclobut-2-en-1-one
• CAS: 216452-15-2
• 化学式: C₁₆H₂₂OSi
• 分子量: 258.436
• InChiKey: SDKCICBDJNAIIW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.46
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.44
• 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-triethylsilylcyclobut-2-en-1-one 生成
  参考文献：
  名称：

  （三烷基甲硅烷基）乙烯基乙烯酮的杂[4 + 2]环加成。α，β-不饱和δ-戊内酯和-内酰胺的合成。

  摘要：

  描述了（三烷基甲硅烷基）乙烯基烯酮（TAS-乙烯基烯酮）与羰基和亚氨基二烯亲和物的杂Diels-Alder反应。TAS-乙烯基乙烯酮与富马二烯作为酮基戊二酸二乙酯参加[4 + 2]环加成反应，以高收率提供α，β-不饱和δ-戊内酯。不可烯化的N-烷基-和N-（三甲基甲硅烷基）亚胺与TAS-乙烯基烯酮结合形成α，β-不饱和δ-戊内酰胺。与大多数涉及未活化亚胺的Diels-Alder反应相反，这些环加成不需要路易斯酸的促进，并且通常以高度的立体选择性进行。

  DOI：

  10.1021/ol9907217
• 作为产物：
  描述：

  triethylsilylphenylethyne 在 锌铜偶 、 四甲基乙二胺 、 溶剂黄146 、 锌 作用下， 以 乙醚 、 乙醇 为溶剂， 反应 18.5h， 生成 3-Phenyl-2-triethylsilylcyclobut-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。
• 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。
• Hetero [4 + 2] Cycloadditions of (Trialkylsilyl)vinylketenes. Synthesis of α,β-Unsaturated δ-Valerolactones and -Lactams
  作者：Dawn M. Bennett、Iwao Okamoto、Rick L. Danheiser

  DOI：10.1021/ol9907217

  日期：1999.8.1

  [formula: see text] Hetero Diels-Alder reactions of (trialkylsilyl)vinylketenes (TAS-vinylketenes) with carbonyl and imino dienophiles are described. TAS-vinylketenes participate as electron-rich dienes in [4 + 2] cycloadditions with diethyl ketomalonate to afford alpha,beta-unsaturated delta-valerolactones in good yield. Nonenolizable N-alkyl- and N-(trimethylsilyl)imines combine with TAS-vinylketenes

  描述了（三烷基甲硅烷基）乙烯基烯酮（TAS-乙烯基烯酮）与羰基和亚氨基二烯亲和物的杂Diels-Alder反应。TAS-乙烯基乙烯酮与富马二烯作为酮基戊二酸二乙酯参加[4 + 2]环加成反应，以高收率提供α，β-不饱和δ-戊内酯。不可烯化的N-烷基-和N-（三甲基甲硅烷基）亚胺与TAS-乙烯基烯酮结合形成α，β-不饱和δ-戊内酰胺。与大多数涉及未活化亚胺的Diels-Alder反应相反，这些环加成不需要路易斯酸的促进，并且通常以高度的立体选择性进行。
• (Trialkylsilyl)vinylketenes:  Synthesis and Application as Diene Components in Diels−Alder Cycloadditions
  作者：Jennifer L. Loebach、Dawn M. Bennett、Rick L. Danheiser

  DOI：10.1021/jo981289u

  日期：1998.11.1

  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.