1-[2-(phenylethynyl)phenyl]-3-(trimethylsilyl)prop-2-yn-1-yl acetate | 1252926-35-4

• 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: 1-[2-(phenylethynyl)phenyl]-3-(trimethylsilyl)prop-2-yn-1-yl acetate
• 英文别名: 1-(2-(phenylethynyl)phenyl)-3-(trimethylsilyl)prop-2-ynyl acetate；[1-[2-(2-Phenylethynyl)phenyl]-3-trimethylsilylprop-2-ynyl] acetate
• CAS: 1252926-35-4
• 化学式: C₂₂H₂₂O₂Si
• 分子量: 346.501
• InChiKey: YITXRQWZOJYDPN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.57
• 重原子数：
  25.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  1-[2-(phenylethynyl)phenyl]-3-(trimethylsilyl)prop-2-yn-1-yl acetate 、 M-TOLYLMAGNESIUM BROMIDE 在 zinc(II) chloride 、 四(三苯基膦)钯 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 14.25h， 以91%的产率得到trimethyl(3-(2-(phenylethynyl)phenyl)-1-m-tolylpropa-1,2-dienyl)silane
  参考文献：
  名称：

  Nonstatistical Dynamic Effects in the Thermal C²–C⁶ Diels–Alder Cyclization of Enyne–Allenes

  摘要：

  The Diels-Alder (DA) reaction channel of the thermal C-2-C-6 (Schmittel) cyclization of enyne-allenes is studied computationally and experimentally evaluating the influence of temperature on product ratios. Remote substituents at the alkyne terminus influence the mechanism of the C-2-C-6/DA cyclization steering it either to a stepwise or a concerted course. Temperature independent product ratios, selectivity of product formation, and computational results obtained at (U)BLYP/6-31G(d) level unveil a mechanism that is strongly controlled by nonstatistical dynamics.

  DOI：

  10.1021/jo302524a
• 作为产物：
  描述：

  2-苯基乙炔基苯甲醛 在 4-二甲氨基吡啶 、 乙基溴化镁 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 1.0h， 生成 1-[2-(phenylethynyl)phenyl]-3-(trimethylsilyl)prop-2-yn-1-yl acetate
  参考文献：
  名称：

  Nonstatistical Dynamic Effects in the Thermal C²–C⁶ Diels–Alder Cyclization of Enyne–Allenes

  摘要：

  The Diels-Alder (DA) reaction channel of the thermal C-2-C-6 (Schmittel) cyclization of enyne-allenes is studied computationally and experimentally evaluating the influence of temperature on product ratios. Remote substituents at the alkyne terminus influence the mechanism of the C-2-C-6/DA cyclization steering it either to a stepwise or a concerted course. Temperature independent product ratios, selectivity of product formation, and computational results obtained at (U)BLYP/6-31G(d) level unveil a mechanism that is strongly controlled by nonstatistical dynamics.

  DOI：

  10.1021/jo302524a

文献信息

• Classical Versus Nonstatistical Behavior in the C²-C6/Ene Cyclization of Enyne-Allenes: Intramolecular Kinetic Isotope Effects and Radical Clock Reactions
  作者：Michael Schmittel、Chandrasekhar Vavilala、Jan Bats

  DOI：10.1055/s-0029-1218799

  日期：2010.7

  The effects of aryl groups on the mechanism of the C²-C6/ene cyclization of enyne-allenes were studied by means of radical clock openings and intramolecular kinetic isotope effects. Upon attachment of a single aryl group at either the alkyne or the allene terminus, the thermal reaction proceeds by a stepwise mechanism that shows significant nonstatistical dynamic effects. Despite this, we were able

  芳基对C²- C 6机理的影响通过自由基钟开口和分子内动力学同位素效应研究了烯炔-丙烯的/烯环化。在炔基或丙二烯末端连接单个芳基后，热反应就通过逐步机理进行，该逐步机理显示出显着的非统计动态效应。尽管如此，我们仍然能够通过使用超快的二苯基环丙基自由基时钟反应来拦截中间的双自由基。当炔基和丙二烯基末端均存在芳基时，分子内动力学同位素效应与经典的逐步机理一致。因此，本研究证明了取决于取代基的反应机理从非统计逐步机理向经典逐步行为的转变。 烯反应-丙二烯-炔烃-自由基反应-闭环-动力学同位素效应
• Quantification of Nonstatistical Dynamics in an Intramolecular Diels–Alder Cyclization without Trajectory Computation
  作者：Debabrata Samanta、Anup Rana、Michael Schmittel

  DOI：10.1021/jo500035b

  日期：2014.3.21

  Experimental and computational (DFT) investigations reveal that enyne-allenes with an aryl group as probe at the allene terminus follow a dynamic non-IRC Diels-Alder cyclization pathway. Starting from two separate C-2-C-6 (Schmittel) transition states (TS), two distinct reaction paths originate that share a common diradical intermediate, however, without mixing! Because the momentum of the initial TS is transmitted into product formation, we suggest a simple protocol without trajectory computations to estimate the fraction of molecules that follow nonstatistical dynamics: It was calculated from the partitioning at the TSs, as derived from DFT computations, and the experimental ratio. The thus-determined percentage of dynamically reacting molecules only slightly depends on the depth of the intermediate well but rather on Delta Delta G double dagger of the initial and the follow-up transition states.