[(1R,2S)-2-penta-1,4-dien-2-yloxycyclohexyl]benzene

• 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: [(1R,2S)-2-penta-1,4-dien-2-yloxycyclohexyl]benzene
• 化学式: C₁₇H₂₂O
• 分子量: 242.361
• InChiKey: RIQRDCXFEFDKJR-SJORKVTESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.41
• 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：

  [(1R,2S)-2-penta-1,4-dien-2-yloxycyclohexyl]benzene 在 镍 吡啶 、 氢气 、 甲铝双(2,6-二叔丁基-4-苯甲醚) 、 碳酸氢钠 作用下， 以 甲苯 为溶剂， 反应 103.0h， 生成 [(1R,2S,3S,5S)-2-acetamido-5-acetyloxy-2-methyl-3-phenylcyclohexyl]methyl acetate
  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：

  氯丙烯镁 、 [(1R,2S)-2-ethynoxycyclohexyl]benzene 在 copper(I) bromide 、 lithium bromide 作用下， 以 四氢呋喃 为溶剂， 反应 1.5h， 以83%的产率得到[(1R,2S)-2-penta-1,4-dien-2-yloxycyclohexyl]benzene
  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. Application to the Synthesis of Aminocarbasugars
  作者：Scott E. Denmark、Martin Juhl

  DOI：10.1002/1522-2675(200211)85:11<3712::aid-hlca3712>3.0.co;2-5

  日期：2002.11

  The tandem inter [4+2]/intra [3+2] cycloaddition of nitroalkenes in the bridged mode was applied to the stereoselective synthesis of β-D-4-amino-2,4-dideoxycarbagulose, a representative aminocarbasugar. The synthesis required only five steps from known materials and delivered the protected aminocarbasugar (−)-20 in excellent yield (see Scheme 9). The success of the synthetic sequence relies on 1) the

  将桥接模式下硝基烯烃的串联间 [4+2]/内 [3+2] 环加成应用于立体选择性合成具有代表性的氨基卡巴糖 β-D-4-amino-2,4-dideoxycarbagulose。该合成只需要从已知材料开始的五个步骤，并以优异的收率提供受保护的氨基卡巴糖 (-)-20（参见方案 9）。合成序列的成功取决于 1) 在硝基烯烃部分掺入 O-取代基的能力，2) 适当修饰的手性亲双烯体的鉴定，特别是 3) 开发特定的实验条件和方案，以允许高度敏感的亚硝基缩醛的形成和分离。(+)-19 的 C(1) 羰基的还原产生了意想不到的立体选择性，
• Tandem Inter [4 + 2]/Intra [3 + 2] Cycloadditions. 6. The Bridged Mode
  作者：Scott E. Denmark、Andreas Stolle、Julie A. Dixon、Vito Guagnano

  DOI：10.1021/ja00112a027

  日期：1995.2
• 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.