5-(2-((三甲基甲硅烷基)乙炔基)苯基)-4-戊炔醛 | 150723-28-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 5-(2-((三甲基甲硅烷基)乙炔基)苯基)-4-戊炔醛
• 英文名称: 5-<2-<(Trimethylsilyl)ethynyl>phenyl>-4-pentynal
• 英文别名: 5-[2-(2-trimethylsilylethynyl)phenyl]pent-4-ynal
• CAS: 150723-28-7
• 化学式: C₁₆H₁₈OSi
• 分子量: 254.404
• InChiKey: OLKCFIFPCQRNFG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.25
• 重原子数：
  18.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  5-(2-((三甲基甲硅烷基)乙炔基)苯基)-4-戊炔醛 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 生成 5-(2-ethynylphenyl)-4-pentynal
  参考文献：
  名称：

  Kinetic and mechanistic studies of the tandem enediyne-radical cyclization

  摘要：

  Enediynes 11 possessing a tethered olefin radical acceptor can participate in a tandem enediyne-radical cyclization to yield dihydrobenzindene derivatives 16. In the present study, the mechanism of this reaction was investigated utilizing kinetic studies to determine whether the mechanism was a radical chain, stepwise, or concerted process. Substrate concentration, 1,4-cyclohexadiene concentration, olefin geometry, and olefin electronics were varied. These experiments demonstrate that the reaction occurs under first-order kinetics over a wide variation in either substrate or 1,4-CHD concentration. The reaction rate is also independent of olefin geometry and olefin electronics. The rate constants for the reactions were similar and ranged from 3.0 X 10(4) s-1 to 6.0 X 10(-4) s-1. The data suggests that the tandem enediyne-radical cyclization proceeds through a distinct 1,4-diyl reactive intermediate such as 5 formed in the rate-determining enediyne cyclization step, followed by a radical cyclization to give 16. The tandem enediyne-radical cyclization mechanism is supported by trapping the intermediate biradical 18 in a tandem enediyne-6-exo-radical cyclization of 17 to give products 19a,b.

  DOI：

  10.1021/jo00072a026
• 作为产物：
  描述：

  1,2-二碘苯 在 copper(l) iodide 、 四(三苯基膦)钯 、 Celite 、 三乙胺 、 pyridinium chlorochromate 作用下， 反应 1.33h， 生成 5-(2-((三甲基甲硅烷基)乙炔基)苯基)-4-戊炔醛
  参考文献：
  名称：

  Synthetic studies of the tandem enediyne-mono- and bisradical cyclizations

  摘要：

  The readily synthesized enediynes 12a-j possessing a tethered olefin radical acceptor can participate in a tandem enediyne-radical cyclization to yield dibydrobenzindene derivatives 14a-j. In the present study, the scope of this reaction was expanded to include a wide variety of olefin acceptors. Substitution at both ends of olefin leads to the formation of two diastereomers 14b and 14c in a 3.5:1 ratio when R3 is Me and R2 is CO2Me. The structures of the dihydrobenzindene products 14b and 14c were confirmed by generating a radical from 25 by a tributyltin hydride reaction which undergoes radical cyclization; this radical is similar to the enediyne-generated radical, which also cyclizes. It was shown that, in 14i and 14j, a substituent at R1 slowed the reaction but still resulted in a good to excellent yield of product. A tandem enediyne-6-exo-radical cyclization of 16 was also carried out but did not work as well as its 5-exo counterpart 12a. Finally, an enediyne 33 containing two olefinic tethers was cyclized in a process to form tetracycle 34 where three rings were formed in one synthetic operation.

  DOI：

  10.1021/ja00078a013

文献信息

• Triggering of the Bergman Cyclization by Photochemical Ring Contraction. Facile Cycloaromatization of Benzannulated Cyclodeca-3,7-diene-1,5-diynes
  作者：Grigori V. Karpov、Vladimir V. Popik

  DOI：10.1021/ja064470q

  日期：2007.4.1

  α-diazo-β-diketone moiety, undergoes efficient light-induced ring contraction to produce two isomeric ten-membered ring enediyne compounds. The latter undergo spontaneous facile Bergman cyclization at or below room temperature. In the photochemical or thermal Wolff rearrangement of 1, the alkyl substituent migrates ca. 2 times faster than the alkynyl group.

  包含 α-重氮-β-二酮部分的十一元环烯二炔 1 经历有效的光诱导环收缩以产生两种异构的十元环烯二炔化合物。后者在室温或低于室温时自发地进行伯格曼环化。在 1 的光化学或热沃尔夫重排中，烷基取代基迁移约。比炔基快2倍。
• Enediyne- and Tributyltin Hydride-Mediated Aryl Radical Additions onto Various Radical Acceptors
  作者：Janet Wisniewski Grissom、Detlef Klingberg、Sabine Meyenburg、Brenda L. Stallman

  DOI：10.1021/jo00104a053

  日期：1994.12

  Tandem enediyne-radical cyclizations were carried out on substrates that contain nitrile and ketone radical accepters. The products of these cyclizations and the previously reported tandem enediyne-radical cyclizations containing aldehyde and oxime ether radical accepters were compared with tributyltin hydride-mediated aryl radical addition reactions with 1-bromonaphthalene derivatives containing aldehyde, oxime ether, nitrile, and ketone radical accepters, since these substrates go through similar initial radical intermediates. Although many of the same products were observed using either method of aryl radical generation, there were distinct differences in the product composition and identity depending on which method was used. These differences can probably be primarily attributed to the temperature difference of the two modes of radical generation.