(1R)-10-(N,N-dimethylaminomethyl)fenchone | 438044-34-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (1R)-10-(N,N-dimethylaminomethyl)fenchone
• 英文别名: (1R)-10-[(dimethylamino)methyl]fenchone；(1S)-10-[(dimethylamino)methyl]fenchone；(1R,4S)-1-[2-(dimethylamino)ethyl]-3,3-dimethylbicyclo[2.2.1]heptan-2-one
• CAS: 438044-34-9
• 化学式: C₁₃H₂₃NO
• 分子量: 209.332
• InChiKey: DYZAARUKCAUMCY-GWCFXTLKSA-N

物化性质

• 沸点：
  270.7±13.0 °C(Predicted)
• 密度：
  0.984±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1R)-10-(N,N-dimethylaminomethyl)fenchone 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 、 二甲基亚砜 为溶剂， 反应 6.0h， 生成 (1R)-(-)-3,3-dimethyl-1-vinyl-2-norbornanone
  参考文献：
  名称：

  A new enantiospecific synthetic procedure to the taxoid-intermediate 10-methylenecamphor, and 10-methylenefenchone

  摘要：

  DOI：

  10.1016/s0957-4166(02)00049-6
• 作为产物：
  描述：

  trifluoro-methanesulfonic acid (1S,4S)-7,7-dimethyl-2-methylene-bicyclo[2.2.1]hept-1-yl ester 在 lithium aluminium tetrahydride 作用下， 以 二氯甲烷 为溶剂， 反应 60.0h， 生成 (1R)-10-(N,N-dimethylaminomethyl)fenchone
  参考文献：
  名称：

  C(10)-Substituted Camphors and Fenchones by Electrophilic Treatment of 2-Methylenenorbornan-1-ols:  Enantiospecificity, Scope, and Limitations

  摘要：

  Valuable chiral sources of C(10)-substituted camphors and C(10)-substituted fenchones can be straightforwardly obtained by treatment of an appropriate, easily obtainable, camphor- or fenchone-derived 2-methylenenorbornan-1-ol with an electrophilic reagent. The process takes place via a tandem regioselective carbon-carbon double-bond addition/stereocontrolled Wagner-Meerwein rearrangement. A complete study of the enantiospecificity, scope, and limitations of this process, as well as about the role played by the hydroxyl group attached at the C(1) bridgehead position of the starting 2-methylenenorbornan-1-ols, has been realized. The feasibility of the described methodology has been exemplified by the highly efficient enantiospecific preparation of several interesting C(10)-halogen-, (C10)-O-, C(10)-S-, C(10)-Se-, or C(10)-C-substituted camphors and fenchones.

  DOI：

  10.1021/jo026566i

文献信息

• Understanding the catalytic role of flexible chiral δ-amino alcohols: the 1-(2-aminoethyl)norbornan-2-ol model
  作者：Antonio García Martínez、Enrique Teso Vilar、Amelia García Fraile、Santiago de la Moya Cerero、Beatriz Lora Maroto

  DOI：10.1016/j.tet.2005.01.108

  日期：2005.3

  knowledge about the structural factors influencing the catalytic behavior of conformationally flexible δ-amino-alcohol-based ligands, for the enantioselective addition of dialkylzincs to prochiral carbonyl groups, has been applied using the 1-(2-aminoethyl)norbornan-2-ol moiety as the model chiral system, and the asymmetrically catalyzed addition of diethylzinc to benzaldehyde as the test reaction

  使用1-（2-氨基乙基）将二烷基锌对映选择性加成到前手性羰基上的经验性第一种方法，即关于影响构象柔性δ-氨基醇基配体催化行为的结构因素的知识降冰片烷-2-醇部分作为模型手性体系，并将二乙基锌不对称催化加成到苯甲醛中作为测试反应。为此，选择了七个基于降冰片烷的手性配体的小型文库，它们带有明确定义的结构变异，可以进行比较研究，即在C（2），C（3）处的相对构型和空间位阻的变异和/或C（7）降冰片烷位置已合成并在上述测试反应中进行了探测。使用非对映异构的Noyori样过渡态对实验结果进行了合理化，表明δ-氨基醇配体的构象柔韧性与经过研究的刚性β-氨基醇相反，在催化反应中起着至关重要的作用。这类配体的行为（不对称过程中的立体化学意义和立体分化程度），这使得这种结构因素对于改进新的相关手性催化剂的设计很重要。从这个意义上讲，提出了一种鲁棒的粗经验模型来预测此类基于δ-氨基醇的配体的催化行为。在这类配
• 2-exo- versus 2-endo-Hydroxyl in δ-amino norbornan-2-ol-based catalysts: investigating the role of the C(2) configuration in the asymmetric induction
  作者：Antonio Garcı́a Martı́nez、Enrique Teso Vilar、Amelia Garcı́a Fraile、Santiago de la Moya Cerero、Beatriz Lora Maroto

  DOI：10.1016/j.tetasy.2003.12.014

  日期：2004.3

  Enantiopure 1-[2-(dimethylamino)ethy]-2,3,3-trimethylnorbornan-2-endo-ol, a new norbornane-based delta-amino alcohol, has been straightforwardly prepared from fenchone. The described route constitutes a model procedure for the preparation of other related C(2)-substituted 6-amino 2-endo-norbornanol ligands. The catalytic activity of the obtained 6-amino 2-endo-norbornanol (for the enantio selective addition of diethylzinc to benzaldehyde) has been compared with that previously described for the corresponding C(2)-epimer, which allows us to study about the role played by the configuration of the hydroxyl-bearing C(2) atom on the catalytic activity. Catalyst models and transition-state models for explaining such a role are proposed and discussed. (C) 2003 Elsevier Ltd. All rights reserved.
• A new enantiospecific synthetic procedure to the taxoid-intermediate 10-methylenecamphor, and 10-methylenefenchone
  作者：Antonio Garcı́a Martı́nez、Enrique Teso Vilar、Amelia Garcı́a Fraile、Santiago de la Moya Cerero、Beatriz Lora Maroto

  DOI：10.1016/s0957-4166(02)00049-6

  日期：2002.2
• C(10)-Substituted Camphors and Fenchones by Electrophilic Treatment of 2-Methylenenorbornan-1-ols:  Enantiospecificity, Scope, and Limitations
  作者：Santiago de la Moya Cerero、Antonio García Martínez、Enrique Teso Vilar、Amelia García Fraile、Beatriz Lora Maroto

  DOI：10.1021/jo026566i

  日期：2003.2.1

  Valuable chiral sources of C(10)-substituted camphors and C(10)-substituted fenchones can be straightforwardly obtained by treatment of an appropriate, easily obtainable, camphor- or fenchone-derived 2-methylenenorbornan-1-ol with an electrophilic reagent. The process takes place via a tandem regioselective carbon-carbon double-bond addition/stereocontrolled Wagner-Meerwein rearrangement. A complete study of the enantiospecificity, scope, and limitations of this process, as well as about the role played by the hydroxyl group attached at the C(1) bridgehead position of the starting 2-methylenenorbornan-1-ols, has been realized. The feasibility of the described methodology has been exemplified by the highly efficient enantiospecific preparation of several interesting C(10)-halogen-, (C10)-O-, C(10)-S-, C(10)-Se-, or C(10)-C-substituted camphors and fenchones.