(dimethylphenylsilyl)ketene | 42414-77-7

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (dimethylphenylsilyl)ketene
• 英文别名: dimethylphenyl silyl ketene；dimethylphenylsilyl ketene；phenyldimethylsilylketene；(Dimethylphenylsilyl)keten
• CAS: 42414-77-7
• 化学式: C₁₀H₁₂OSi
• 分子量: 176.29
• InChiKey: UPTZBRWFNWISLV-UHFFFAOYSA-N

物化性质

• 沸点：
  45-46 °C(Press: 1.5 Torr)
• 密度：
  0.9806 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  1.53
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.2
• 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：

  (dimethylphenylsilyl)ketene 在 水 作用下， 以 氘代乙腈 为溶剂， 反应 14.0h， 生成 二甲基苯基甲硅烷基乙酸
  参考文献：
  名称：

  Phenyldimethylsilyl-Substituted Ketenes and Bisketenes

  摘要：

  The phenyldimethylsilyl-substituted monoketene PhMe(2)SiCH=C=O (1) and bisketene (PhMe(2)SiC=C=O)(2) (3) have been prepared and compared to the corresponding Me(3)Si- and t-BuMe(2)Si-substituted species. The C-13, O-17, and Si-29 NMR spectra fit the pattern shown by other silylketenes and provide no evidence for transmission of a substituent effect of the Ph group through the silicon to the ketenyl group, as has been proposed for PhMe(2)Si-substituted radicals. The UV spectrum of 1 does show a longer lambda and greater epsilon than for t-BuMe(2)SiCH=C=O, and this may indicate some interaction of the phenyl group with the ketene chromophore, while the greater reactivity of 1 in hydration compared to t-BuMe(2)SiCH=C=O is ascribed to the inductive effect of the phenyl. The very similar ring-opening reactivity of the bis(phenyldimethylsilyl)cyclobutenedione (6) to form 3 compared to the bis(Me(3)Si) analogues also provides no evidence of a significant interaction of the phenyl with the ketene. A new type of stabilized 1,8-bisketene based on the arylbis(dimethylsilyl) grouping, namely, 1,4-bis(ketenyldimethylsilyl)benzene (12), has been prepared for the first time.

  DOI：

  10.1021/jo9605197
• 作为产物：
  描述：

  (Dimethylphenylsilyl)acetylchlorid 在 三乙胺 作用下， 以 乙醚 为溶剂， 生成 (dimethylphenylsilyl)ketene
  参考文献：
  名称：

  Kostyuk,A.S. et al., Journal of general chemistry of the USSR, 1979, vol. 49, p. 1346 - 1353

  摘要：

  DOI：

文献信息

• Lewis Acid-Activated Reactions of Silyl Ketenes for the Preparation of α-Silyl Carbonyl Compounds
  作者：Sarah M. Mitchell、Yuanhui Xiang、Rachael Matthews、Alexis M. Amburgey、Emily B. Pentzer

  DOI：10.1021/acs.joc.9b01859

  日期：2019.11.15

  Silyl-substituted ketenes are attractive molecular building blocks due to their stability and ease of storage, as opposed to unstable alkyl and aryl ketenes. To better understand the reactivity of silyl ketenes and, in turn, their use in the preparation of highly functionalized small molecules, the reaction of silyl ketenes with different nucleophiles was studied. The addition of alcohol, amine, or

  与不稳定的烷基和芳基乙烯酮相反，甲硅烷基取代的乙烯酮由于其稳定性和易于储存而成为有吸引力的分子构建基。为了更好地理解甲硅烷基烯酮的反应性，进而将其用于制备高度官能化的小分子，研究了甲硅烷基烯酮与不同亲核试剂的反应。将醇，胺或硫醇亲核试剂添加到甲硅烷基烯酮的中心碳上，然后进行质子转移，分别得到α-甲硅烷基酯，酰胺或硫代酯。催化量的路易斯酸大大提高了反应速率，并评估了亲核试剂，路易斯酸和甲硅烷基取代基的影响。由这些反应产生的小分子使人们深入了解了甲硅烷基烯酮作为复杂分子结构的基础。
• <i>C</i>₂-Symmetric Cu(II) Complexes as Chiral Lewis Acids. Catalytic, Enantioselective Cycloadditions of Silyl Ketenes
  作者：David A. Evans、Jacob M. Janey

  DOI：10.1021/ol016096z

  日期：2001.6.1

  [reaction: see text] C(2)-Symmetric bis(oxazoline)-Cu(II) complexes (4a-g) catalyze the enantioselective [2 + 2] cycloaddition between (silyl)ketenes and chelating carbonyl substrates. A range of substituted beta-lactones can be produced in excellent yields and selectivities. It was also found that (trimethylsilyl)ketene (1) may also undergo a highly selective hetero Diels-Alder reaction with beta

  [反应：见正文] C（2）-对称的双（恶唑啉）-Cu（II）配合物（4a-g）催化（甲硅烷基）烯酮与螯合羰基底物之间的对映选择性[2 + 2]环加成反应。可以以优异的产率和选择性生产一系列取代的β-内酯。还发现（三甲基甲硅烷基）乙烯酮（1）也可能与β，γ-不饱和的α-酮酯发生高度选择性的杂Diels-Alder反应。
• Amination of Ketenes:  Kinetic and Mechanistic Studies
  作者：Annette D. Allen、Thomas T. Tidwell

  DOI：10.1021/jo982054l

  日期：1999.1.1

  contrast to previous studies of Ph(2)C=C=O and other reactive ketenes in which only a first-order dependence on [amine] was observed in H(2)O or in CH(3)CN. Derived third-order rate constants for 6 depend on the amine basicity, with a 1.7 x 10(7) greater reactivity for n-BuNH(2) compared to CF(3)CH(2)NH(2). These kinetic results are consistent with recently reported theoretical studies for reaction of CH(2)=C=O

  与之形成鲜明对比的是，PhMe（2）SiCH = C = O（6）与胺在CH（3）CN中形成酰胺反应的速率常数最适合与[胺]混合的二阶和三阶依赖性以前对Ph（2）C = C = O和其他反应性烯酮的研究，其中在H（2）O或CH（3）CN中仅观察到对[胺]的一级依赖。派生的6的三阶速率常数取决于胺的碱性，与CF（3）CH（2）NH（2）相比，n-BuNH（2）具有1.7 x 10（7）更大的反应性。这些动力学结果与最近报道的CH（2）= C = O与NH（3）反应的理论研究相一致。对于6，在CH（3）CN中的相对反应性k（n-BuNH（2））/ k（H（2）O）估计为10（13）。拥挤的乙烯酮t-Bu（2）C = C = O（10）极易失活并发生胺化反应，在纯正n-BuNH（2）中的反应速率比10-12慢10（12）和2 x 10（5）倍。 t-BuCH = C = O和t-BuC（i-Pr）=
• Addition of Bromine to Ketenes and Bisketenes:  Electrophilic Attack at Carbonyl Carbon and Neighboring Group Participation
  作者：R. S. Brown、Manfred Christl、Alan J. Lough、Jihai Ma、Eva-Maria Peters、Karl Peters、Frank Sammtleben、Henryka Slebocka-Tilk、Kuangsen Sung、Thomas T. Tidwell

  DOI：10.1021/jo980684h

  日期：1998.8.1

  Addition of bromine to bisketene (Me(3)SiC=C=O)(2) (1) gave the fumaryl dibromide E-7, whose stereochemistry was proven by X-ray structure determination. Upon warming, E-7 rearranged to the furanone 8, and this process was faster in the more polar CD(3)CN compared to CDCl(3), consistent with an ionization pathway for the rearrangement. The bromination of 1 in CH(2)ClCH(2)Cl followed second-order kinetics

  将溴添加到双烯酮中（Me（3）SiC = C = O）（2）（1）得到富马酰二溴化物E-7，其立体化学通过X射线结构测定得到证实。加热后，E-7重排至呋喃酮8，与CDCl（3）相比，极性更大的CD（3）CN中此过程更快，这与重排的电离途径一致。CH（2）ClCH（2）Cl中1的溴化反应遵循二级动力学，速率常数为（2.1 +/- 0.1）x 10（4）M（-）（1）s（-）（1） 25°C。向[Br（2）]上添加1的溴的一阶依赖性归因于分子内的亲核助剂，该分子是由第二个烯基部分在1和Br（2）的初始配合物中得到E-7形成的。从头算方法已经计算出该过程的过渡结构。相比之下，PhMe（2）SiCH = C = O 11和γ-氧杂环丁烯16通过三级动力学进行溴化，在[Br（2）]中为二级，表明在限速步骤中不存在相邻基团。双烯酮Me（2）Si（CH = C = O）（2）（13）通过混合动力学与[Br（2）]中的一阶和二阶项进行溴化。
• Chemistry of silylketenes: a simple preparation of α-silyl-α-stannylacetic esters and their stereoselective Reformatsky-type reaction with aldehydes or aldimines
  作者：Shuji Akai、Yasunori Tsuzuki、Satoshi Matsuda、Shinji Kitagaki、Yasuyuki Kita

  DOI：10.1039/p19920002813

  日期：——

  Silylketenes 1a, b reacted smoothly with alkoxystannanes 3 to give the corresponding alpha-silyl-alpha-stannylacetates 4 almost quantitatively. Treatment of 4 with TiCl4 caused selective cleavage of the C-Sn bond to bring about Reformatsky-type reaction with aldehydes 6 giving beta-hydroxy-alpha-silyl esters 7. These two steps were carried out by one-pot operation, and variously substituted compounds 7 were obtained with high syn-selectivity (52-> 96% d.e.) in 41-89% yields. A similar one-pot procedure starting from la-c, 3, and aldimines 11 also provided the corresponding beta-amino-alpha-silyl esters 12 with excellent syn-selectivity (greater-than-or-equal-to 96% d.e.) in 64-94% yields. Stereocontrolled preparation of both (E)- and (Z)-alpha,beta-unsaturated esters 8 and a syn-amino diol derivative 17 from syn-7 and syn-12, respectively, is also described.