trans-3-Methyl-5-phenyl-1-methylidenecyclohexane | 28467-40-5

• 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: trans-3-Methyl-5-phenyl-1-methylidenecyclohexane
• 英文别名: trans-3-methyl-5-phenylcyclohexanone；trans-3-Methyl-5-phenylcyclohexenon；(3S,5S)-3-methyl-5-phenylcyclohexan-1-one
• CAS: 28467-40-5
• 化学式: C₁₃H₁₆O
• 分子量: 188.269
• InChiKey: UXNQEKBXCVHUOD-JQWIXIFHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  trans-3-Methyl-5-phenyl-1-methylidenecyclohexane 以 乙醇 、 苯 为溶剂， 生成
  参考文献：
  名称：

  Retention of configuration at the migrating atom in the photochemical 1,3-allylic shift of a benzyl group

  摘要：

  DOI：

  10.1021/ja00838a032
• 作为产物：
  描述：

  4-Phenyl-6-phenylsulfanylmethyl-hept-6-en-2-ol 在 吡啶 、 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 20.0h， 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

文献信息

• Chemistry of higher order, mixed organocuprates. reactions of α,β-unsaturated ketones.
  作者：Bruce H. Lipshutz、Robert S. Wilhelm、Joseph Kozlowski

  DOI：10.1016/s0040-4039(00)87698-4

  日期：1982.1

  Organocuprates of general formula R2Cu(CN)Li2 react rapidly with α,β-unsaturated ketones at low temperatures and in high yields to deliver ligands in a conjugate manner. These reagents apparently do not require the use of additives for stabilizing or solubilizing purposes.

  通式R 2 Cu（CN）Li 2的有机化合物在低温下以高收率与α，β-不饱和酮迅速反应，以共轭方式递送配体。这些试剂显然不需要为了稳定或增溶目的而使用添加剂。
• Reactions involving electron transfer. II. Reductions of enones with alkali metal solutions
  作者：Herbert O. House、Roger W. Giese、Karlheinz Kronberger、Jean P. Kaplan、Joseph F. Simeone

  DOI：10.1021/ja00712a033

  日期：1970.5
• Chemistry of higher order, mixed organocuprates. 5. On the choice of the copper(I) salt for the formation of R2CuLi
  作者：Bruce H. Lipshutz、Joseph A. Kozlowski、Robert S. Wilhelm

  DOI：10.1021/jo00152a026

  日期：1983.2
• Kinetic Resolution of Chiral Cyclohex-2-enones by Rhodium(I)/binap-Catalyzed 1,2- and 1,4-Additions
  作者：Andreas Kolb、Sebastian Hirner、Klaus Harms、Paultheo von Zezschwitz

  DOI：10.1021/ol300387f

  日期：2012.4.20

  The feasibility of kinetic resolutions of racemic monosubstituted cyclohex-2-enones by Rh/binap-catalyzed reactions was investigated. 1,2-Addition of AlMe3 to the 5-substituted derivatives furnished allylic alcohols in the matched case, while the less reactive enantiomers were either left over or transformed into trans-3,5-disubstituted cyclohexanones in parallel or sequential 1,4-additions. Altogether, these represent regiodivergent reactions on racemic mixtures. In contrast, 1,4-addition of aryl groups led to inferior results since either catalyst or substrate control dominated.
• [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.