7-<(Bromomethyl)dimethylsilyloxy>-7-methyl-1-octen-5-yne | 130747-91-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 7-<(Bromomethyl)dimethylsilyloxy>-7-methyl-1-octen-5-yne
• 英文别名: Bromomethyl-dimethyl-(2-methyloct-7-en-3-yn-2-yloxy)silane
• CAS: 130747-91-0
• 化学式: C₁₂H₂₁BrOSi
• 分子量: 289.288
• InChiKey: JCGJCSZYXXCTCB-UHFFFAOYSA-N

物化性质

• 沸点：
  281.4±30.0 °C(Predicted)
• 密度：
  1.111±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.89
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  7-<(Bromomethyl)dimethylsilyloxy>-7-methyl-1-octen-5-yne 在 偶氮二异丁腈 、 三苯基氢化锡 、 双氧水 、 potassium hydrogencarbonate 作用下， 以 四氢呋喃 、 甲醇 、 苯 为溶剂， 反应 8.0h， 生成 (E)-3-Methyl-2-(3-pentenylidene)-1,3-butanediol
  参考文献：
  名称：

  Radical cyclization of (bromomethyl)dimethylsilyl propargyl ethers. Regio-, chemo- and stereoselectivity.

  摘要：

  Radical cyclization of (bromomethyl)dimethylsilyl propargyl ether derivatives 1 is a powerful reaction with a high degree of regio-, chemo-, and stereoselectivity. Trisubstituted olefins 3, cyclopentene derivatives 5, and diquinane system 7j are obtained in good yields by a judicious choice of unsaturated substituents. Triquinane frameworks could be obtained stereoselectively from a suitable acyclic substrate of type 1 in a one-pot reaction. First attempts have not yet allowed us to aim at this goal due to interesting (1,5) hydrogen transfers. Moreover, we have intercepted, for the first time, the alpha-cyclopropyl radical which is involved in the Stork-Beckwith mechanism of the 5-versus 6-membered ring formation in the vinyl radical cyclization.

  DOI：

  10.1021/jo00037a026
• 作为产物：
  描述：

  2-甲基-3-丁炔-2-醇 在 4-二甲氨基吡啶 、 正丁基锂 、 四丁基氟化铵 、 对甲苯磺酸 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 0.25h， 生成 7-<(Bromomethyl)dimethylsilyloxy>-7-methyl-1-octen-5-yne
  参考文献：
  名称：

  Radical cyclization of (bromomethyl)dimethylsilyl propargyl ethers. Regio-, chemo- and stereoselectivity.

  摘要：

  Radical cyclization of (bromomethyl)dimethylsilyl propargyl ether derivatives 1 is a powerful reaction with a high degree of regio-, chemo-, and stereoselectivity. Trisubstituted olefins 3, cyclopentene derivatives 5, and diquinane system 7j are obtained in good yields by a judicious choice of unsaturated substituents. Triquinane frameworks could be obtained stereoselectively from a suitable acyclic substrate of type 1 in a one-pot reaction. First attempts have not yet allowed us to aim at this goal due to interesting (1,5) hydrogen transfers. Moreover, we have intercepted, for the first time, the alpha-cyclopropyl radical which is involved in the Stork-Beckwith mechanism of the 5-versus 6-membered ring formation in the vinyl radical cyclization.

  DOI：

  10.1021/jo00037a026

文献信息

• Radical cyclization of (bromomethyl)dimethylsilyl propargyl ethers regioselective intramolecular cyclization of vinyl radicals.
  作者：Michel Journet、Elisabeth Magnol、Gilbert Agnel、Max Malacria

  DOI：10.1016/s0040-4039(00)97644-5

  日期：1990.1

  Vinyl radical intermediates generated from radical cyclization of (bromomethyl)dimethylsilyl propargyl ethers have been trapped intramolecularly by a double bond leading to functionalized carbocycles with high yield and high regiosclectivity.

  由（溴甲基）二甲基甲硅烷基炔丙基醚的自由基环化产生的乙烯基自由基中间体已通过双键被分子内俘获，从而以高收率和高区域弯曲性导致官能化的碳环。
• JOURNET, MICHEL;MAGNOL, ELISABETH;AGNEL, GILBERT;MALACRIA, MAX, TETRAHEDRON LETT., 31,(1990) N1, C. 4445-4448
  作者：JOURNET, MICHEL、MAGNOL, ELISABETH、AGNEL, GILBERT、MALACRIA, MAX

  DOI：——

  日期：——