1-(2-azido-phenyl)-3-(4,4-dimethyl-3-triisopropylsilanyloxy-cyclohex-enyl)-prop-2-ynyl acetate | 1020202-96-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 1-(2-azido-phenyl)-3-(4,4-dimethyl-3-triisopropylsilanyloxy-cyclohex-enyl)-prop-2-ynyl acetate
• 英文别名: [1-(2-Azidophenyl)-3-[4,4-dimethyl-3-tri(propan-2-yl)silyloxycyclohexen-1-yl]prop-2-ynyl] acetate
• CAS: 1020202-96-3
• 化学式: C₂₈H₄₁N₃O₃Si
• 分子量: 495.737
• InChiKey: ASHLADHDHFBIQN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.54
• 重原子数：
  35
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  49.9
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1-(2-azido-phenyl)-3-(4,4-dimethyl-3-triisopropylsilanyloxy-cyclohex-enyl)-prop-2-ynyl acetate 、 甲基溴化镁 在 copper(l) iodide 、 lithium bromide 、 水 、 氯化铵 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 1.0h， 以89%的产率得到{3-[3-(2-azido-phenyl)-1-methyl-propa-1,2-dienyl]-6,6-dimethyl-cyclohex-2-enyloxy}-triisopropyl-silane
  参考文献：
  名称：

  Allenyl Azide Cycloaddition Chemistry. Photochemical Initiation and CuI Mediation Leads to Improved Regioselectivity

  摘要：

  Irradiation of 2-(3-alkenyl)allenylphenyl azides in the presence of excess Cul furnished functionalized 2,3-cyclopentenylindoles in good yield with only trace amounts of competitive C-N-bonded regioisomeric products. These results represent a significant departure from the modestto-nonexistent regioselectivity that attended thermal cyclization of these allenyl azide substrates.

  DOI：

  10.1021/ol800429j
• 作为产物：
  描述：

  1-(2-azido-phenyl)-prop-2-ynyl acetate 、 (3-iodo-6,6-dimethyl-cyclohex-2-enyloxy)-triisopropylsilane 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 16.0h， 以92%的产率得到1-(2-azido-phenyl)-3-(4,4-dimethyl-3-triisopropylsilanyloxy-cyclohex-enyl)-prop-2-ynyl acetate
  参考文献：
  名称：

  Allenyl Azide Cycloaddition Chemistry. Photochemical Initiation and CuI Mediation Leads to Improved Regioselectivity

  摘要：

  Irradiation of 2-(3-alkenyl)allenylphenyl azides in the presence of excess Cul furnished functionalized 2,3-cyclopentenylindoles in good yield with only trace amounts of competitive C-N-bonded regioisomeric products. These results represent a significant departure from the modestto-nonexistent regioselectivity that attended thermal cyclization of these allenyl azide substrates.

  DOI：

  10.1021/ol800429j

文献信息

• Allenyl Azide Cycloaddition Chemistry. 2,3-Cyclopentennelated Indole Synthesis through Indolidene Intermediates
  作者：Ken S. Feldman、D. Keith Hester、Malliga R. Iyer、Paul J. Munson、Carlos Silva López、Olalla Nieto Faza

  DOI：10.1021/jo900659w

  日期：2009.7.17

  The thermal, photochemical, and photochemical/CuI-mediated cascade cyclizations of a range of substituted 1-(2-azidophenyl)-3-alkenylallenes are described. These reactions provide both 1,2- and 2,3-cyclopentennelated indole products in varying ratios. In most cases, high regioselectivity for the 2,3-annelated isomer can be achieved under the hv/CuI conditions. Computational studies of this multistep reaction support the intermediacy of indolidene intermediates whose electrocyclizations (with or without copper present) define the regioselectivity branch point in the sequence.