1-[(4aR,9aS)-2,4a,9,9a-tetrahydroindeno[2,1-b][1,4]oxazin-4-ium-3-yl]-2-(2,3,4,5,6-pentafluorophenyl)hydrazine;tetrafluoroborate | 862095-87-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚满类
• 英文名称: 1-[(4aR,9aS)-2,4a,9,9a-tetrahydroindeno[2,1-b][1,4]oxazin-4-ium-3-yl]-2-(2,3,4,5,6-pentafluorophenyl)hydrazine;tetrafluoroborate
• CAS: 862095-87-2
• 化学式: BF₄*C₁₇H₁₂F₅N₃O*H
• 分子量: 457.106
• InChiKey: IMFGBQIXULDANS-QDOFGCGHSA-O

计算性质

• 辛醇/水分配系数(LogP)：
  3.67
• 重原子数：
  31
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  50.2
• 氢给体数：
  2
• 氢受体数：
  13

反应信息

• 作为反应物：
  描述：

  1-[(4aR,9aS)-2,4a,9,9a-tetrahydroindeno[2,1-b][1,4]oxazin-4-ium-3-yl]-2-(2,3,4,5,6-pentafluorophenyl)hydrazine;tetrafluoroborate 、 原甲酸三乙酯 以 氯苯 为溶剂， 反应 12.0h， 生成
  参考文献：
  名称：

  Oxyanion Steering and CH−π Interactions as Key Elements in an N-Heterocyclic Carbene-Catalyzed [4 + 2] Cycloaddition

  摘要：

  The N-heterocyclic carbene catalyzed [4 + 2] cycloaddition has been shown to give gamma,delta-unsaturated delta-lactones in excellent enantio- and diastereoselectivity. However, preliminary computational studies of the geometry of the intermediate enolate rendered ambiguous both the origins of selectivity and the reaction pathway. Here, we show that a concerted, but highly asynchronous, Diels-Alder reaction occurs rather than the stepwise Michael-type or Claisen-type pathways. In addition, two crucial interactions are identified that enable high selectivity an oxyanion-steering mechanism and a CH-pi interaction. The calculations accurately predict the enantioselectivity of a number of N-heterocyclic carbene catalysts in the hetero-Diels-Alder reaction.

  DOI：

  10.1021/ja302761d
• 作为产物：
  描述：

  、 五氨基氟丙基氢氧吡啶 以 二氯甲烷 为溶剂， 反应 3.0h， 生成 1-[(4aR,9aS)-2,4a,9,9a-tetrahydroindeno[2,1-b][1,4]oxazin-4-ium-3-yl]-2-(2,3,4,5,6-pentafluorophenyl)hydrazine;tetrafluoroborate
  参考文献：
  名称：

  Oxyanion Steering and CH−π Interactions as Key Elements in an N-Heterocyclic Carbene-Catalyzed [4 + 2] Cycloaddition

  摘要：

  The N-heterocyclic carbene catalyzed [4 + 2] cycloaddition has been shown to give gamma,delta-unsaturated delta-lactones in excellent enantio- and diastereoselectivity. However, preliminary computational studies of the geometry of the intermediate enolate rendered ambiguous both the origins of selectivity and the reaction pathway. Here, we show that a concerted, but highly asynchronous, Diels-Alder reaction occurs rather than the stepwise Michael-type or Claisen-type pathways. In addition, two crucial interactions are identified that enable high selectivity an oxyanion-steering mechanism and a CH-pi interaction. The calculations accurately predict the enantioselectivity of a number of N-heterocyclic carbene catalysts in the hetero-Diels-Alder reaction.

  DOI：

  10.1021/ja302761d

文献信息

• Oxyanion Steering and CH−π Interactions as Key Elements in an N-Heterocyclic Carbene-Catalyzed [4 + 2] Cycloaddition
  作者：Scott E. Allen、Jessada Mahatthananchai、Jeffrey W. Bode、Marisa C. Kozlowski

  DOI：10.1021/ja302761d

  日期：2012.7.25

  The N-heterocyclic carbene catalyzed [4 + 2] cycloaddition has been shown to give gamma,delta-unsaturated delta-lactones in excellent enantio- and diastereoselectivity. However, preliminary computational studies of the geometry of the intermediate enolate rendered ambiguous both the origins of selectivity and the reaction pathway. Here, we show that a concerted, but highly asynchronous, Diels-Alder reaction occurs rather than the stepwise Michael-type or Claisen-type pathways. In addition, two crucial interactions are identified that enable high selectivity an oxyanion-steering mechanism and a CH-pi interaction. The calculations accurately predict the enantioselectivity of a number of N-heterocyclic carbene catalysts in the hetero-Diels-Alder reaction.