(+/-)-3-<(tert-Butyldimethylsilyl)oxy>-1-dodecyne | 157488-51-2

• 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: (+/-)-3-<(tert-Butyldimethylsilyl)oxy>-1-dodecyne
• 英文别名: Tert-butyl-dodec-1-yn-3-yloxy-dimethylsilane
• CAS: 157488-51-2
• 化学式: C₁₈H₃₆OSi
• 分子量: 296.569
• InChiKey: KWWONUIAZGAMLV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.15
• 重原子数：
  20
• 可旋转键数：
  11
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (+/-)-3-<(tert-Butyldimethylsilyl)oxy>-1-dodecyne 在 Pd-BaSO₄ 正丁基锂 、 氢气 作用下， 以 四氢呋喃 、 吡啶 、 正己烷 为溶剂， 反应 24.0h， 生成 (+/-)-(7Z)-9-<(tert-Butyldimethylsilyl)oxy>-2-methyl-7-octadecen-6-ol
  参考文献：
  名称：

  Synthesis and Inhibitory Properties of Pheromone Analogs for the Epoxide Hydrolase of the Gypsy Moth

  摘要：

  A series of analogues of disparlure, the gypsy moth (Lymantria dispar) sex attractant, was synthesized, and the potency of these inhibitors in suppressing the metabolism of disparlure by the L. dispar epoxide hydrolase (EH) was determined. The analogues substituted at the 6-position (6-hydroxy-, 6-oxo-, and 6,6-difluorodisparlure; (+/-)-threo,cis-11, (+/-)-13, and (+/-)-17, respectively), along with 9,9-difluorodisparlure [(+/-)-26], were the most potent inhibitors (IC50 values of 4-9 mu M). Two other 9-substituted analogues, 9-hydroxydisparlure [(+/-)-threo,cis-21] and 9-oxodisparlure [(+/-)-22], were slightly less potent (IC50 values of 18 and 30 mu M, respectively). Analogues substituted at both the 6- and 9-positions (threo,erythro-6,9-dihydroxy-, threo,threo-6,9-dihydroxy-, and 6,9-dioxodisparlure; (+/-)-threo,erythro-32, (+/-)-threo,threo-32, and (+/-)-33, respectively) were generally the least potent inhibitors (IC50 values of 27-200 mu M). On the basis of a model of the EH active site, a hypothesis is advanced to rationalize the higher potencies of the 6-substituted analogues. Pheromone metabolism plays a key role in pheromone perception, and the potential consequences of inhibition of pheromone metabolism are discussed.

  DOI：

  10.1021/jo00090a012
• 作为产物：
  描述：

  1-dodecyn-3-ol 、 叔丁基二甲基氯硅烷 在 咪唑 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 20.0h， 以73%的产率得到(+/-)-3-<(tert-Butyldimethylsilyl)oxy>-1-dodecyne
  参考文献：
  名称：

  Synthesis and Inhibitory Properties of Pheromone Analogs for the Epoxide Hydrolase of the Gypsy Moth

  摘要：

  A series of analogues of disparlure, the gypsy moth (Lymantria dispar) sex attractant, was synthesized, and the potency of these inhibitors in suppressing the metabolism of disparlure by the L. dispar epoxide hydrolase (EH) was determined. The analogues substituted at the 6-position (6-hydroxy-, 6-oxo-, and 6,6-difluorodisparlure; (+/-)-threo,cis-11, (+/-)-13, and (+/-)-17, respectively), along with 9,9-difluorodisparlure [(+/-)-26], were the most potent inhibitors (IC50 values of 4-9 mu M). Two other 9-substituted analogues, 9-hydroxydisparlure [(+/-)-threo,cis-21] and 9-oxodisparlure [(+/-)-22], were slightly less potent (IC50 values of 18 and 30 mu M, respectively). Analogues substituted at both the 6- and 9-positions (threo,erythro-6,9-dihydroxy-, threo,threo-6,9-dihydroxy-, and 6,9-dioxodisparlure; (+/-)-threo,erythro-32, (+/-)-threo,threo-32, and (+/-)-33, respectively) were generally the least potent inhibitors (IC50 values of 27-200 mu M). On the basis of a model of the EH active site, a hypothesis is advanced to rationalize the higher potencies of the 6-substituted analogues. Pheromone metabolism plays a key role in pheromone perception, and the potential consequences of inhibition of pheromone metabolism are discussed.

  DOI：

  10.1021/jo00090a012

文献信息

• Stereoselective, Cascade Synthesis of <i>trans</i>-Enynones through Coupling-Isomerization Reaction
  作者：Bhavani Shankar Chinta、Beeraiah Baire

  DOI：10.1021/acs.joc.5b01780

  日期：2015.10.16

  A mild, cascade methodology based on the modified Cadiot-Chodkiewicz reaction was developed for the stereoselective synthesis of trans-enynones. By this methodology, structurally divergent trans-enynones, which are embedded with sensitive functional groups, were synthesized. Control experiments suggested that the CuCl alone does not have a role in the isomerization step, whereas the CuCl piperidine complex (formed during the cross coupling) may have a rate enhancing effect. Furthermore, additional sets of control experiments favor the involvement of unimolecular [1,2]-H shift rather than a homobimolecular proton abstraction during the isomerization step.
• Synthesis and Inhibitory Properties of Pheromone Analogs for the Epoxide Hydrolase of the Gypsy Moth
  作者：Steven M. Graham、Glenn D. Prestwich

  DOI：10.1021/jo00090a012

  日期：1994.6

  A series of analogues of disparlure, the gypsy moth (Lymantria dispar) sex attractant, was synthesized, and the potency of these inhibitors in suppressing the metabolism of disparlure by the L. dispar epoxide hydrolase (EH) was determined. The analogues substituted at the 6-position (6-hydroxy-, 6-oxo-, and 6,6-difluorodisparlure; (+/-)-threo,cis-11, (+/-)-13, and (+/-)-17, respectively), along with 9,9-difluorodisparlure [(+/-)-26], were the most potent inhibitors (IC50 values of 4-9 mu M). Two other 9-substituted analogues, 9-hydroxydisparlure [(+/-)-threo,cis-21] and 9-oxodisparlure [(+/-)-22], were slightly less potent (IC50 values of 18 and 30 mu M, respectively). Analogues substituted at both the 6- and 9-positions (threo,erythro-6,9-dihydroxy-, threo,threo-6,9-dihydroxy-, and 6,9-dioxodisparlure; (+/-)-threo,erythro-32, (+/-)-threo,threo-32, and (+/-)-33, respectively) were generally the least potent inhibitors (IC50 values of 27-200 mu M). On the basis of a model of the EH active site, a hypothesis is advanced to rationalize the higher potencies of the 6-substituted analogues. Pheromone metabolism plays a key role in pheromone perception, and the potential consequences of inhibition of pheromone metabolism are discussed.