(1R*,1'R*)-4-<1'-Hydroxybenzyl>cyclohex-3-enyl methyl ketone

• 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*,1'R*)-4-<1'-Hydroxybenzyl>cyclohex-3-enyl methyl ketone
• 英文别名: 1-[(1S)-4-[(S)-hydroxy(phenyl)methyl]cyclohex-3-en-1-yl]ethanone
• 化学式: C₁₅H₁₈O₂
• 分子量: 230.307
• InChiKey: JBTZVPUGXWHQLD-IUODEOHRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1R*,1'R*)-4-<1'-Hydroxybenzyl>cyclohex-3-enyl methyl ketone 在 manganese(IV) oxide 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 以90%的产率得到4-Acetylcyclohex-1-enyl phenyl ketone
  参考文献：
  名称：

  Thermal and Catalyzed Diels-Alder Reactions with Chiral 2-Substituted-1,3-dienes: Conformational Models for Diastereofacial Selectivity

  摘要：

  The thermal or BF3-catalyzed Diels-Alder reactions of chiral 2-substituted-1,3-dienes bearing a hydroxy or a protected hydroxy group at the allylic position with various dienophiles have been studied in order to determine the regio- and stereoselective control elements. Good regio- and facial selectivities were ob;served in thermal reaction of dienes bearing a free hydroxy group. The stereoselectivity was reversed and strongly lowered when the hydroxy soup was protected as an ether. However the regio- as well as the stereoselectivity of the cycloaddition of these diene ethers with alpha,beta-unsaturated aldehydes or ketones are remarkably enhanced by the addition of a Lewis acid since in a few cases a unique isomer was formed. These experimental results have been rationalized and could be explained by conformational preferences of the dienes in the transition state. In particular, the reversal of facial selectivity for dienes having a free hydroxy group has been attributed to a hydrogen bonding interaction between the diene and the dienophile.

  DOI：

  10.1021/jo00094a029
• 作为产物：
  描述：

  (1R*,1'R*)-4-<1'-<(Trimethylsilyl)oxy>benzyl>cyclohex-3-enyl methyl ketone 在 盐酸 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以87%的产率得到(1R*,1'R*)-4-<1'-Hydroxybenzyl>cyclohex-3-enyl methyl ketone
  参考文献：
  名称：

  Thermal and Catalyzed Diels-Alder Reactions with Chiral 2-Substituted-1,3-dienes: Conformational Models for Diastereofacial Selectivity

  摘要：

  The thermal or BF3-catalyzed Diels-Alder reactions of chiral 2-substituted-1,3-dienes bearing a hydroxy or a protected hydroxy group at the allylic position with various dienophiles have been studied in order to determine the regio- and stereoselective control elements. Good regio- and facial selectivities were ob;served in thermal reaction of dienes bearing a free hydroxy group. The stereoselectivity was reversed and strongly lowered when the hydroxy soup was protected as an ether. However the regio- as well as the stereoselectivity of the cycloaddition of these diene ethers with alpha,beta-unsaturated aldehydes or ketones are remarkably enhanced by the addition of a Lewis acid since in a few cases a unique isomer was formed. These experimental results have been rationalized and could be explained by conformational preferences of the dienes in the transition state. In particular, the reversal of facial selectivity for dienes having a free hydroxy group has been attributed to a hydrogen bonding interaction between the diene and the dienophile.

  DOI：

  10.1021/jo00094a029

文献信息

• Thermal and Catalyzed Diels-Alder Reactions with Chiral 2-Substituted-1,3-dienes: Conformational Models for Diastereofacial Selectivity
  作者：Robert Bloch、Nathalie Chaptal-Gradoz

  DOI：10.1021/jo00094a029

  日期：1994.7

  The thermal or BF3-catalyzed Diels-Alder reactions of chiral 2-substituted-1,3-dienes bearing a hydroxy or a protected hydroxy group at the allylic position with various dienophiles have been studied in order to determine the regio- and stereoselective control elements. Good regio- and facial selectivities were ob;served in thermal reaction of dienes bearing a free hydroxy group. The stereoselectivity was reversed and strongly lowered when the hydroxy soup was protected as an ether. However the regio- as well as the stereoselectivity of the cycloaddition of these diene ethers with alpha,beta-unsaturated aldehydes or ketones are remarkably enhanced by the addition of a Lewis acid since in a few cases a unique isomer was formed. These experimental results have been rationalized and could be explained by conformational preferences of the dienes in the transition state. In particular, the reversal of facial selectivity for dienes having a free hydroxy group has been attributed to a hydrogen bonding interaction between the diene and the dienophile.