4-Phenyl-6-phenylsulfanylmethyl-hept-6-en-2-one | 172978-85-7

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 4-Phenyl-6-phenylsulfanylmethyl-hept-6-en-2-one
• 英文别名: 4-Phenyl-6-(phenylsulfanylmethyl)hept-6-en-2-one
• CAS: 172978-85-7
• 化学式: C₂₀H₂₂OS
• 分子量: 310.46
• InChiKey: HQPOAYYEIFBCBC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  22
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  42.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-Phenyl-6-phenylsulfanylmethyl-hept-6-en-2-one 在 吡啶 、 Oxone 、 sodium tetrahydroborate 、 二苯甲酮 、 六甲基二锡 、 lithium bromide 作用下， 以 四氢呋喃 、 氘代苯 为溶剂， 反应 13.0h， 生成 trans-3-Methyl-5-phenyl-1-methylidenecyclohexane
  参考文献：
  名称：

  [3 + 3] Annulation Based on 6-Endo-Trig Radical Cyclization: Regioselectivity and Diastereoselectivity

  摘要：

  The development of a [3 + 3] annulation strategy based on sequential ''two-electron'' and ''one-electron'' allylation of beta-substituted aldehydes and derivatives with the bifunctional isobutene conjunctive reagent 1 is described. The key step involves an unusual 6-endo-trig radical cyclization. Yields of 6-endo products are improved if the PhS group is oxidized to a PhSO(2) group prior to cyclization. The structural factors affecting the regioselectivity and stereoselectivity of the cyclization are examined. In general, the stereoselectivity of 6-endo-trig cyclization of 5-hexenyl radicals can be rationalized by conformational analysis of chairlike transition states and can be calculated effectively with an MM2 force field model, High 6-endo regioselectivity requires a strong driving force. Fragmentable allylic groups (R(3)Sn, PhSO(2), and to a lesser extent PhS) are shown to be sufficiently activating to achieve 6-endo regioselectivity.

  DOI：

  10.1021/jo00129a024
• 作为产物：
  描述：

  <2-<(phenylthio)methyl>allyl>trimethylsilane 、 苄叉丙酮 在 四氯化钛 作用下， 以44%的产率得到4-Phenyl-6-phenylsulfanylmethyl-hept-6-en-2-one
  参考文献：
  名称：

  [3 + 3] Annulation Based on 6-Endo-Trig Radical Cyclization: Regioselectivity and Diastereoselectivity

  摘要：

  The development of a [3 + 3] annulation strategy based on sequential ''two-electron'' and ''one-electron'' allylation of beta-substituted aldehydes and derivatives with the bifunctional isobutene conjunctive reagent 1 is described. The key step involves an unusual 6-endo-trig radical cyclization. Yields of 6-endo products are improved if the PhS group is oxidized to a PhSO(2) group prior to cyclization. The structural factors affecting the regioselectivity and stereoselectivity of the cyclization are examined. In general, the stereoselectivity of 6-endo-trig cyclization of 5-hexenyl radicals can be rationalized by conformational analysis of chairlike transition states and can be calculated effectively with an MM2 force field model, High 6-endo regioselectivity requires a strong driving force. Fragmentable allylic groups (R(3)Sn, PhSO(2), and to a lesser extent PhS) are shown to be sufficiently activating to achieve 6-endo regioselectivity.

  DOI：

  10.1021/jo00129a024

文献信息

• [3 + 3] Annulation Based on 6-Endo-Trig Radical Cyclization: Regioselectivity and Diastereoselectivity
  作者：Dale E. Ward、Yuanzhu Gai、Brian F. Kaller

  DOI：10.1021/jo00129a024

  日期：1995.12

  The development of a [3 + 3] annulation strategy based on sequential ''two-electron'' and ''one-electron'' allylation of beta-substituted aldehydes and derivatives with the bifunctional isobutene conjunctive reagent 1 is described. The key step involves an unusual 6-endo-trig radical cyclization. Yields of 6-endo products are improved if the PhS group is oxidized to a PhSO(2) group prior to cyclization. The structural factors affecting the regioselectivity and stereoselectivity of the cyclization are examined. In general, the stereoselectivity of 6-endo-trig cyclization of 5-hexenyl radicals can be rationalized by conformational analysis of chairlike transition states and can be calculated effectively with an MM2 force field model, High 6-endo regioselectivity requires a strong driving force. Fragmentable allylic groups (R(3)Sn, PhSO(2), and to a lesser extent PhS) are shown to be sufficiently activating to achieve 6-endo regioselectivity.