3-[3-(2-azido-phenyl)-1-methyl-propa-1,2-dienyl]-1-(tert-butyl-dimethyl-silanyloxy)-6,6-dimethyl-cyclohex-2-enecarbonitrile | 1020202-77-0

• 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: 3-[3-(2-azido-phenyl)-1-methyl-propa-1,2-dienyl]-1-(tert-butyl-dimethyl-silanyloxy)-6,6-dimethyl-cyclohex-2-enecarbonitrile
• CAS: 1020202-77-0
• 化学式: C₂₅H₃₄N₄OSi
• 分子量: 434.657
• InChiKey: KBYLWJPFRCONGD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.22
• 重原子数：
  31.0
• 可旋转键数：
  5.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  81.78
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  3-[3-(2-azido-phenyl)-1-methyl-propa-1,2-dienyl]-1-(tert-butyl-dimethyl-silanyloxy)-6,6-dimethyl-cyclohex-2-enecarbonitrile 在 copper(l) iodide 作用下， 以 乙腈 为溶剂， 以62%的产率得到10-(tert-butyl-dimethyl-silanyloxy)-6,9,9-trimethyl-5,7,8,9,10,10a-hexahydro-indeno[2,1-b]indole-10-carbonitrile
  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：

  acetic acid 1-(2-azido-phenyl)-3-[3-(tert-butyl-dimethyl-silanyloxy)-3-cyano-4,4-dimethyl-cyclohex-1-enyl]-prop-2-ynyl ester 、 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81%的产率得到3-[3-(2-azido-phenyl)-1-methyl-propa-1,2-dienyl]-1-(tert-butyl-dimethyl-silanyloxy)-6,6-dimethyl-cyclohex-2-enecarbonitrile
  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.