3-(trimethylsilyl)-1-[2-(2-phenylethynyl)phenyl]prop-2-yn-1-ol | 879286-37-0

• 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-(trimethylsilyl)-1-[2-(2-phenylethynyl)phenyl]prop-2-yn-1-ol
• 英文别名: 1-(2-(phenylethynyl)phenyl)-3-(trimethylsilyl)prop-2-yn-1-ol；1-[2-(phenylethynyl)phenyl]-3-(trimethylsilyl)prop-2-yn-1-ol；1-[2-(2-phenylethynyl)phenyl]-3-trimethylsilylprop-2-yn-1-ol
• CAS: 879286-37-0
• 化学式: C₂₀H₂₀OSi
• 分子量: 304.464
• InChiKey: FADDVCKWGXJDSY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.0
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3-(trimethylsilyl)-1-[2-(2-phenylethynyl)phenyl]prop-2-yn-1-ol 在 氢氧化钾 作用下， 以 甲醇 为溶剂， 以98%的产率得到1-(2-(phenylethynyl)phenyl)prop-2-yn-1-ol
  参考文献：
  名称：

  在烯炔-丙二烯thermolyses空间效应：切换从迈尔斯齐藤反应到C 2 C 6 -cyclization和DNA链切割

  摘要：

  烯炔-丙二烯的热反应1具有大取代基（叔在乙炔末端引线到C -丁基，三甲基甲硅烷）2 C 6环化产物可能通过中间benzofulvene双自由基与氢取代基的预期迈尔斯齐藤cycloaromatization，而产品形成。当没有分子内途径可用时，可以观察到有效的DNA链断裂。

  DOI：

  10.1016/0040-4039(96)01758-3
• 作为产物：
  描述：

  2-碘苯甲醛 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 乙基溴化镁 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 16.5h， 生成 3-(trimethylsilyl)-1-[2-(2-phenylethynyl)phenyl]prop-2-yn-1-ol
  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

• TRACELESS DIRECTING GROUPS IN RADICAL CASCADES: FROM OLIGOALKYNES TO FUSED HELICENES WITHOUT TETHERED INITATORS
  申请人：The Florida State University Research Foundation, Inc.

  公开号：US20160145276A1

  公开（公告）日：2016-05-26

  The present disclosure is directed to a traceless directing group in a radical cascade. The chemo- and regioselectivity of the initial attack in skipped oligoalkynes is controlled by a propargyl alkoxy moiety. Radical translocations lead to the boomerang return of radical center to the site of initial attack where it assists to the elimination of the directing functionality via β-scission in the last step of the cascade. In some aspects, the reaction of the present invention is catalyzed by a stannane moiety, which allows further via facile reactions with electrophiles as well as Stille and Suzuki cross-coupling reactions. This selective radical transformation opens a new approach for the controlled transformation of skipped oligoalkynes into polycyclic ribbons of tunable dimensions.

  本公开涉及一种在自由基级联中无痕定向基团。跳跃寡炔烃中的初始攻击的化学和区域选择性由丙炔烯氧基团控制。自由基转位导致自由基中心回到初始攻击点的回旋，它在级联的最后一步中通过β-裂解协助消除定向功能。在某些方面，本发明的反应由一种锡烷基团催化，它允许通过与亲电试剂以及Stille和Suzuki交叉偶联反应的简便反应进一步进行。这种选择性的自由基转化为控制跳跃寡炔烃转化为可调尺寸的多环核糖带提供了一种新方法。
• The thermal C2–C6/[2 + 2] cyclisation of enyne-allenes: Reversible diradical formation
  作者：Mehmet Emin Cinar、Chandrasekhar Vavilala、Jian Fan、Michael Schmittel

  DOI：10.1039/c0ob01275k

  日期：——

  structurally designed toward the thermal C2–C6/[2 + 2] cyclisation mode, were prepared and characterised, one of them even by X-ray crystallography. The mechanism of their transformation to formal [2 + 2] cycloadducts was interrogated by trapping experiments and DFT computations. The results support a stepwise mechanism that involves the reversible formation of the C2–C6 diradical intermediate.

  制备并表征了针对热C 2 -C 6 / [2 + 2]环化模式结构设计的新烯炔-丙烯，其中之一甚至通过X射线晶体学进行表征。通过诱捕实验和DFT计算研究了它们转化为正式的[2 + 2]环加合物的机理。结果支持逐步机理，该机理涉及C 2 -C 6双自由基中间体的可逆形成。
• A new rearrangement of cyclic allenes via 1,2-dehydro[10]annulenes: formation of benzo[c]fluorenones
  作者：David Rodrı́guez、Armando Navarro-Vázquez、Luis Castedo、Domingo Domı́nguez、Carlos Saá

  DOI：10.1016/s0040-4039(02)00368-4

  日期：2002.4

  A new rearrangement of cyclic allenes giving benzo[c]fluorenones was observed when studying intramolecular dehydro Diels–Alder reactions of silyl-substituted alkynes with arenynes (aryldiacetylenes).

  当研究甲硅烷基取代的炔烃与芳烃（芳基二乙炔）的分子内脱氢狄尔斯-阿尔德反应时，观察到一种新的环状Allenes重排生成苯并[ c ]芴酮。
• Synthesis and Inclusion Properties of 6,6′-Bi(benzo[<i>b</i>]fluoren-5-ol) Derivative by Cycloaromatization
  作者：Tomikazu Kawano、Masako Suehiro、Ikuo Ueda

  DOI：10.1246/cl.2006.58

  日期：2006.1

  Aromatic non-conjugated tetraynes underwent step-by-step cycloaromatization to yield 6,6′-bi(benzo[b]fluoren-5-ol) derivative 1 via benzo[b]fluoren-5-ol derivatives. Treatment of compound 1 with a kind of organic guest compounds afforded crystalline inclusion compounds (clathrates).

  通过苯并[b]芴-5-醇衍生物，芳香族非共轭四炔逐步发生环芳香化反应，生成 6,6′-双（苯并[b]芴-5-醇）衍生物 1。用一种有机客体化合物对化合物 1 进行处理，可得到结晶包合物（clathrates）。
• 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