methyl 1-(2-methylphenyl)oct-2-yn-1-yl carbonate | 849927-49-7

• 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: methyl 1-(2-methylphenyl)oct-2-yn-1-yl carbonate
• 英文别名: methyl 1-(2-methylphenyl)oct-2-ynyl carbonate
• CAS: 849927-49-7
• 化学式: C₁₇H₂₂O₃
• 分子量: 274.36
• InChiKey: PPFKEXBGLDCOLJ-UHFFFAOYSA-N

物化性质

• 沸点：
  381.6±42.0 °C(Predicted)
• 密度：
  1.037±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  20.0
• 可旋转键数：
  5.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  methyl 1-(2-methylphenyl)oct-2-yn-1-yl carbonate 、 邻苯二酚 在 tris(dibenzylideneacetone)dipalladium (0) 三乙胺 、 1,4-双(二苯基膦)丁烷 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 生成 (2Z)-2-hexylidene-3-(2-methylphenyl)-2,3-dihydro-1,4-benzodioxin 、 (2Z)-2-(2-methylbenzylidene)-3-pentyl-2,3-dihydro-1,4-benzodioxin
  参考文献：
  名称：

  Asymmetric palladium-catalyzed annulation of benzene-1,2-diol and racemic secondary propargylic carbonates bearing two different substituents

  摘要：

  The palladium-catalyzed cyclization of benzene-1,2-diol with various racemic secondary propargyl carbonates having no acetylenic hydrogen in the presence of (R)-Binap as the chiral ligand afforded the two regioisomers of the corresponding 2,3-dihydro-1,4-dioxin derivatives in quite good yields, and also in enantioselectivities going from 40 to 97%. The cyclization of benzene-1,2-diol with methyl (R)-1-methyl-3-phenylpro-2-yn-1-yl carbonate in the presence of dppb as the achiral ligand afforded 2-benzylidene-3-methyl-2,3-dihydro-1,4-benzodioxine as the major product with 15% ee. The use of (R)-Binap as the chiral ligand afforded the (+) cyclized compound in 45% ee, when the (-) enantiomer was obtained with 77% ee in the presence of (S)-Binap. All the results suggest that in this case the enantioselective step is the diastereoselective protonation of the palladium-carbene intermediates. (C) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.01.084
• 作为产物：
  描述：

  2-甲基苯甲醛 在 吡啶 、 4-二甲氨基吡啶 、 N,N-二甲基丙烯基脲 、 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 48.0h， 生成 methyl 1-(2-methylphenyl)oct-2-yn-1-yl carbonate
  参考文献：
  名称：

  Asymmetric palladium-catalyzed annulation of benzene-1,2-diol and racemic secondary propargylic carbonates bearing two different substituents

  摘要：

  The palladium-catalyzed cyclization of benzene-1,2-diol with various racemic secondary propargyl carbonates having no acetylenic hydrogen in the presence of (R)-Binap as the chiral ligand afforded the two regioisomers of the corresponding 2,3-dihydro-1,4-dioxin derivatives in quite good yields, and also in enantioselectivities going from 40 to 97%. The cyclization of benzene-1,2-diol with methyl (R)-1-methyl-3-phenylpro-2-yn-1-yl carbonate in the presence of dppb as the achiral ligand afforded 2-benzylidene-3-methyl-2,3-dihydro-1,4-benzodioxine as the major product with 15% ee. The use of (R)-Binap as the chiral ligand afforded the (+) cyclized compound in 45% ee, when the (-) enantiomer was obtained with 77% ee in the presence of (S)-Binap. All the results suggest that in this case the enantioselective step is the diastereoselective protonation of the palladium-carbene intermediates. (C) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.01.084