methyl (R)-1-methylprop-2-yn-1-yl carbonate | 849927-61-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机碳酸及其衍生物
• 英文名称: methyl (R)-1-methylprop-2-yn-1-yl carbonate
• 英文别名: [(2R)-but-3-yn-2-yl] methyl carbonate
• CAS: 849927-61-3
• 化学式: C₆H₈O₃
• 分子量: 128.128
• InChiKey: YJKZFCWYRWPDRB-RXMQYKEDSA-N

物化性质

• 沸点：
  129.0±23.0 °C(Predicted)
• 密度：
  1.054±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  9
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  邻苯二酚 、 methyl (R)-1-methylprop-2-yn-1-yl carbonate 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， 生成 (+)-2,3-dihydro-2-methyl-3-methylene-1,4-benzodioxin 、 (3Z)-3-ethylidene-1,4-benzodioxine
  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：

  (R)-(+)-3-丁炔-2-醇 、 氯甲酸甲酯 在 吡啶 、 4-二甲氨基吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以82%的产率得到methyl (R)-1-methylprop-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