(1'S,4R,6R,11'R)-4,6-dimethylspiro[1,3-dioxane-2,13'-bicyclo[9.3.1]pentadecane]-12'-one

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1'S,4R,6R,11'R)-4,6-dimethylspiro[1,3-dioxane-2,13'-bicyclo[9.3.1]pentadecane]-12'-one
• 化学式: C₂₀H₃₄O₃
• 分子量: 322.488
• InChiKey: BRBNWUXAHUVZEF-ZJPYXAASSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  23
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1'S,4R,6R,11'R)-4,6-dimethylspiro[1,3-dioxane-2,13'-bicyclo[9.3.1]pentadecane]-12'-one 在 lithium aluminium tetrahydride 作用下， 生成 (1'S,4R,6R,11'R,12'R)-4,6-dimethylspiro[1,3-dioxane-2,13'-bicyclo[9.3.1]pentadecane]-12'-ol 、 (1'S,4R,6R,11'R,12'S)-4,6-dimethylspiro[1,3-dioxane-2,13'-bicyclo[9.3.1]pentadecane]-12'-ol
  参考文献：
  名称：

  Asymmetric functionalization of conformationally distinctive Cs-symmetric cis-[n.3.1] bicyclic ketones. Definition of the absolute course of enantio- and diastereodifferentiation

  摘要：

  The four C(s)-symmetric cis[n.3.1] bicyclic ketones where n = 3, 5, 7, and 9 were acetalized with (R,R)-2,4-pentanediol, and the resulting derivatives were cleaved with triisobutylaluminum (TRIBAL). The first three examples, all of which have their polymethylene chain rigidly fixed in a diaxial orientation, undergo ring opening with very high diastereoselectivity to give 5. In the fourth case (n = 9), the chain is sufficiently long to be attached in a diequatorial manner. The response of 4d to TRIBAL is to deliver a 1:1 mixture of 11 and 12. The stereochemical course of epoxidation and cyclopropanation reactions of these enol ethers has been assessed. Where 5 and 11 are concerned, these functionalization reactions are 100% pi-facially selective. Only 12 is the exception. Also examined in this study was the enantioselective deprotonation of the same ketones with the enantiomerically pure lithium amide base 27. The resulting enolates were trapped as their silyl enol ethers and transformed directly into optically active alpha-hydroxy ketones and alpha,beta-unsaturated enones by epoxidation and selenenylation-oxidative elimination, respectively. The sense of the observed enantioselectivity was the same irrespective of the diaxial or diequatorial disposition of the (CH2)n loop. However, the asymmetry induced by this means was consistently opposite to that realized by TRIBAL-promoted acetal cleavage. When these complementary processes are compared at the alpha-hydroxy ketone stage, the acetal cleavage-epoxidation option was invariably 100% enantioselective; greater variability in optical purity was seen via the deprotonation-silylation-epoxidation option. The possible mechanistic basis of these observations is explored.

  DOI：

  10.1021/jo00046a028
• 作为产物：
  描述：

  cis-bicyclo<9.3.1>pentadecan-12-one 在 草酰氯 、 collidinium p-toluene sulfonate 、 三异丁基铝 、 三乙胺 、 间氯过氧苯甲酸 作用下， 以 甲苯 为溶剂， 反应 2.75h， 生成 (1'S,4R,6R,11'R)-4,6-dimethylspiro[1,3-dioxane-2,13'-bicyclo[9.3.1]pentadecane]-12'-one
  参考文献：
  名称：

  Asymmetric functionalization of conformationally distinctive Cs-symmetric cis-[n.3.1] bicyclic ketones. Definition of the absolute course of enantio- and diastereodifferentiation

  摘要：

  The four C(s)-symmetric cis[n.3.1] bicyclic ketones where n = 3, 5, 7, and 9 were acetalized with (R,R)-2,4-pentanediol, and the resulting derivatives were cleaved with triisobutylaluminum (TRIBAL). The first three examples, all of which have their polymethylene chain rigidly fixed in a diaxial orientation, undergo ring opening with very high diastereoselectivity to give 5. In the fourth case (n = 9), the chain is sufficiently long to be attached in a diequatorial manner. The response of 4d to TRIBAL is to deliver a 1:1 mixture of 11 and 12. The stereochemical course of epoxidation and cyclopropanation reactions of these enol ethers has been assessed. Where 5 and 11 are concerned, these functionalization reactions are 100% pi-facially selective. Only 12 is the exception. Also examined in this study was the enantioselective deprotonation of the same ketones with the enantiomerically pure lithium amide base 27. The resulting enolates were trapped as their silyl enol ethers and transformed directly into optically active alpha-hydroxy ketones and alpha,beta-unsaturated enones by epoxidation and selenenylation-oxidative elimination, respectively. The sense of the observed enantioselectivity was the same irrespective of the diaxial or diequatorial disposition of the (CH2)n loop. However, the asymmetry induced by this means was consistently opposite to that realized by TRIBAL-promoted acetal cleavage. When these complementary processes are compared at the alpha-hydroxy ketone stage, the acetal cleavage-epoxidation option was invariably 100% enantioselective; greater variability in optical purity was seen via the deprotonation-silylation-epoxidation option. The possible mechanistic basis of these observations is explored.

  DOI：

  10.1021/jo00046a028

文献信息

• Asymmetric functionalization of conformationally distinctive Cs-symmetric cis-[n.3.1] bicyclic ketones. Definition of the absolute course of enantio- and diastereodifferentiation
  作者：Theodore L. Underiner、Leo A. Paquette

  DOI：10.1021/jo00046a028

  日期：1992.9

  The four C(s)-symmetric cis[n.3.1] bicyclic ketones where n = 3, 5, 7, and 9 were acetalized with (R,R)-2,4-pentanediol, and the resulting derivatives were cleaved with triisobutylaluminum (TRIBAL). The first three examples, all of which have their polymethylene chain rigidly fixed in a diaxial orientation, undergo ring opening with very high diastereoselectivity to give 5. In the fourth case (n = 9), the chain is sufficiently long to be attached in a diequatorial manner. The response of 4d to TRIBAL is to deliver a 1:1 mixture of 11 and 12. The stereochemical course of epoxidation and cyclopropanation reactions of these enol ethers has been assessed. Where 5 and 11 are concerned, these functionalization reactions are 100% pi-facially selective. Only 12 is the exception. Also examined in this study was the enantioselective deprotonation of the same ketones with the enantiomerically pure lithium amide base 27. The resulting enolates were trapped as their silyl enol ethers and transformed directly into optically active alpha-hydroxy ketones and alpha,beta-unsaturated enones by epoxidation and selenenylation-oxidative elimination, respectively. The sense of the observed enantioselectivity was the same irrespective of the diaxial or diequatorial disposition of the (CH2)n loop. However, the asymmetry induced by this means was consistently opposite to that realized by TRIBAL-promoted acetal cleavage. When these complementary processes are compared at the alpha-hydroxy ketone stage, the acetal cleavage-epoxidation option was invariably 100% enantioselective; greater variability in optical purity was seen via the deprotonation-silylation-epoxidation option. The possible mechanistic basis of these observations is explored.