2-[(+/-)-(2,2-diphenylcyclopentyl)oxy]-1,4-pentadiene | 191937-70-9

• 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: 2-[(+/-)-(2,2-diphenylcyclopentyl)oxy]-1,4-pentadiene
• 英文别名: (2-Penta-1,4-dien-2-yloxy-1-phenylcyclopentyl)benzene
• CAS: 191937-70-9
• 化学式: C₂₂H₂₄O
• 分子量: 304.432
• InChiKey: PUVNRLUKCTTXLN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  23
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.27
• 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：

  反式硝基苯乙烯 、 2-[(+/-)-(2,2-diphenylcyclopentyl)oxy]-1,4-pentadiene 在 四氯化锡 作用下， 以 甲苯 为溶剂， 反应 0.25h， 以83%的产率得到6-(2,2-Diphenylcyclopentyl)oxy-2-oxido-4-phenyl-6-prop-2-enyl-4,5-dihydrooxazin-2-ium
  参考文献：
  名称：

  Tandem Inter [4 + 2]/Intra [3 + 2] Cycloadditions of Nitroalkenes. 15. The Bridged Mode (α-Tether)

  摘要：

  A new variant of the tandem inter [4 + 2]/intra [3 + 2] cycloaddition of nitroalkenes is described in detail. The scope and limitations of the bridged mode tandem cycloaddition in which the diene and dienophile are part of the same molecule are documented. Simple 1,4-pentadienes as well as 2-alkoxy-1,4-pentadienes can function effectively as dienophile and dipolarophile combinations with excellent chemical selectivity and regio- and diastereoselectivities. Hydrogenation of the bridged nitroso acetals produces aminocyclohexanemethanol derivatives in high diastereo- and enantioselectivities. Further, insights into the mechanistic aspects of the Raney nickel promoted hydrogenation are reported. An intriguing influence of the nitro olefin alpha-substituent on the diastereoselectivity in the [4 + 2] cycloaddition has been documented. The reactivity of the alpha-chlorosubstituted nitroalkene 26 as the heterodiene in the Diels-Alder reaction is assayed, and the use of the chlorine atom as a hydrogen surrogate is described.

  DOI：

  10.1021/jo970686m
• 作为产物：
  描述：

  2,2-diphenylcyclopentanol 在 正丁基锂 、 potassium hydride 、 copper(I) bromide 、 lithium bromide 作用下， 以 四氢呋喃 为溶剂， 反应 18.5h， 生成 2-[(+/-)-(2,2-diphenylcyclopentyl)oxy]-1,4-pentadiene
  参考文献：
  名称：

  Tandem Inter [4 + 2]/Intra [3 + 2] Cycloadditions of Nitroalkenes. 15. The Bridged Mode (α-Tether)

  摘要：

  A new variant of the tandem inter [4 + 2]/intra [3 + 2] cycloaddition of nitroalkenes is described in detail. The scope and limitations of the bridged mode tandem cycloaddition in which the diene and dienophile are part of the same molecule are documented. Simple 1,4-pentadienes as well as 2-alkoxy-1,4-pentadienes can function effectively as dienophile and dipolarophile combinations with excellent chemical selectivity and regio- and diastereoselectivities. Hydrogenation of the bridged nitroso acetals produces aminocyclohexanemethanol derivatives in high diastereo- and enantioselectivities. Further, insights into the mechanistic aspects of the Raney nickel promoted hydrogenation are reported. An intriguing influence of the nitro olefin alpha-substituent on the diastereoselectivity in the [4 + 2] cycloaddition has been documented. The reactivity of the alpha-chlorosubstituted nitroalkene 26 as the heterodiene in the Diels-Alder reaction is assayed, and the use of the chlorine atom as a hydrogen surrogate is described.

  DOI：

  10.1021/jo970686m

文献信息

• Tandem Inter [4 + 2]/Intra [3 + 2] Cycloadditions of Nitroalkenes. 15. The Bridged Mode (α-Tether)
  作者：Scott E. Denmark、Vito Guagnano、Julie A. Dixon、Andreas Stolle

  DOI：10.1021/jo970686m

  日期：1997.7.1

  A new variant of the tandem inter [4 + 2]/intra [3 + 2] cycloaddition of nitroalkenes is described in detail. The scope and limitations of the bridged mode tandem cycloaddition in which the diene and dienophile are part of the same molecule are documented. Simple 1,4-pentadienes as well as 2-alkoxy-1,4-pentadienes can function effectively as dienophile and dipolarophile combinations with excellent chemical selectivity and regio- and diastereoselectivities. Hydrogenation of the bridged nitroso acetals produces aminocyclohexanemethanol derivatives in high diastereo- and enantioselectivities. Further, insights into the mechanistic aspects of the Raney nickel promoted hydrogenation are reported. An intriguing influence of the nitro olefin alpha-substituent on the diastereoselectivity in the [4 + 2] cycloaddition has been documented. The reactivity of the alpha-chlorosubstituted nitroalkene 26 as the heterodiene in the Diels-Alder reaction is assayed, and the use of the chlorine atom as a hydrogen surrogate is described.