3-<(Bromomethyl)dimethylsilyloxy>-3-methyl-1-phenyl-1-butyne | 133678-97-4

• 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-<(Bromomethyl)dimethylsilyloxy>-3-methyl-1-phenyl-1-butyne
• 英文别名: Bromomethyl-dimethyl-(2-methyl-4-phenylbut-3-yn-2-yl)oxysilane
• CAS: 133678-97-4
• 化学式: C₁₄H₁₉BrOSi
• 分子量: 311.294
• InChiKey: JTERCVUVBXMCFZ-UHFFFAOYSA-N

物化性质

• 沸点：
  324.6±22.0 °C(Predicted)
• 密度：
  1.19±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.97
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 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-<(Bromomethyl)dimethylsilyloxy>-3-methyl-1-phenyl-1-butyne 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 2-benzylidene-3-methylbutane-1,3-diol
  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：

  溴甲基二甲基氯硅烷 、 2-甲基-4-苯基-3-丁炔-2-醇 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 0.25h， 生成 3-<(Bromomethyl)dimethylsilyloxy>-3-methyl-1-phenyl-1-butyne
  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 Bromomethyldimethylsilyl Propargyl Ethers; a General Method for the Stereoselective Synthesis of Variously Substituted Trimethylenemethane (TMM) Precursors
  作者：Stéphane Bogen、Michel Journet、Max Malacria

  DOI：10.1080/00397919408011720

  日期：1994.5

  Abstract The radical cyclization of bromomethyldimethylsilyl propargyl ethers allows the regio- and stereoselective preparation of variously substituted 2-trimethylsilylmethyl-2-propen-1-ol derivatives in good yields. After acetylation of the alcohol function, these compounds are useful precursors of trimethylene-methane (TMM) in [3+2] cycloaddition reactions using the Trost methodology.

  摘要 溴甲基二甲基甲硅烷基炔丙基醚的自由基环化允许以良好的产率区域和立体选择性地制备各种取代的 2-三甲基甲硅烷基甲基-2-丙烯-1-醇衍生物。在醇官能团乙酰化后，这些化合物在使用 Trost 方法的 [3+2] 环加成反应中是三亚甲基甲烷 (TMM) 的有用前体。
• Bogen Stephane, Journet Michel, Malacria Max, Synth. Commun., 24 (1994) N 9, S 1215-1221
  作者：Bogen Stephane, Journet Michel, Malacria Max

  DOI：——

  日期：——