methyl 7-(2-(3-(tert-butyldimethylsiloxy)propynyl)phenyl)-1-hept-2-en-6-ynoate | 150723-20-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: methyl 7-(2-(3-(tert-butyldimethylsiloxy)propynyl)phenyl)-1-hept-2-en-6-ynoate
• 英文别名: methyl 7-{2-[3-(tert-butyldimethylsiloxy)propynyl]phenyl}-1-hept-2-en-6-ynoate；methyl (E)-7-[2-[3-[tert-butyl(dimethyl)silyl]oxyprop-1-ynyl]phenyl]hept-2-en-6-ynoate
• CAS: 150723-20-9
• 化学式: C₂₃H₃₀O₃Si
• 分子量: 382.575
• InChiKey: QNKSRMDNBPJRMW-VCHYOVAHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.92
• 重原子数：
  27
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl 7-(2-(3-(tert-butyldimethylsiloxy)propynyl)phenyl)-1-hept-2-en-6-ynoate 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 以98%的产率得到methyl 7-<2-(3-hydroxy-1-propynyl)phenyl>hept-2-en-6-ynoate
  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
• 作为产物：
  描述：

  1,2-二碘苯 在 copper(l) iodide 、 四(三苯基膦)钯 、 Celite 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三乙胺 、 pyridinium chlorochromate 、 lithium chloride 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 生成 methyl 7-(2-(3-(tert-butyldimethylsiloxy)propynyl)phenyl)-1-hept-2-en-6-ynoate
  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

• Kinetic and mechanistic studies of the tandem enediyne-radical cyclization
  作者：Janet Wisniewski Grissom、Trevor L. Calkins

  DOI：10.1021/jo00072a026

  日期：1993.9

  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.