(S)-2-(bis(4-(dimethylamino)phenyl)methyl)cyclohexanone | 1220284-22-9

• 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: (S)-2-(bis(4-(dimethylamino)phenyl)methyl)cyclohexanone
• 英文别名: (2S)-2-[bis[4-(dimethylamino)phenyl]methyl]cyclohexan-1-one
• CAS: 1220284-22-9
• 化学式: C₂₃H₃₀N₂O
• 分子量: 350.504
• InChiKey: OCGQUBZKGDYTNQ-OAQYLSRUSA-N

物化性质

• 沸点：
  516.8±40.0 °C(Predicted)
• 密度：
  1.091±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  26
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  23.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  米氏酮 在 sodium tetrahydroborate 、 C₁₉H₁₈N₂OS 、 四氯化钛 、 三乙胺 、 三氟乙酸 作用下， 以 乙醇 、 二氯甲烷 、 1,2-二氯乙烷 为溶剂， 反应 90.0h， 生成 (S)-2-(bis(4-(dimethylamino)phenyl)methyl)cyclohexanone 、 (R)-2-(bis(4-(dimethylamino)phenyl)methyl)cyclohexanone
  参考文献：
  名称：

  Catalytic Asymmetric α-Alkylation of Ketones and Aldehydes with N-Benzylic Sulfonamides through Carbon–Nitrogen Bond Cleavage

  摘要：

  A range of ketones and aldehydes smoothly undergo asymmetric S(N)1 alpha-alkylation with N-benzylic sulfonamides in the presence of 10 mol % of a chiral imidazolidinone and trifluoroacetic acid to give the corresponding products in good to excellent yields and with good enantioselectivity. This chemistry has been successfully extended to the asymmetric desymmetrization of 4-substituted cyclohexanones, which exhibits greater than 99:1 diastereoselectivity and good enantioselectivity.

  DOI：

  10.1021/jo2014142

文献信息

• 4-Fluoro and 4-Hydroxy Pyrrolidine-thioxotetrahydropyrimidinones: Organocatalysts for Green Asymmetric Transformations in Brine
  作者：Nikolaos Kaplaneris、Giorgos Koutoulogenis、Marianna Raftopoulou、Christoforos G. Kokotos

  DOI：10.1021/acs.joc.5b00283

  日期：2015.6.5

  The synthesis of both trans- and cis-diastereomers of pyrrolidinine-thioxotetrahydropyrimidinone bearing either a fluorine or a hydroxyl group was accomplished. The new compounds were tested for their catalytic properties in a variety of asymmetric organic transformations and compared with the first generation catalyst. It was found that the new catalysts could efficiently catalyze the reactions in

  两者的合成反式-和顺pyrrolidinine-thioxotetrahydropyrimidinone轴承任一个氟或羟基的-diastereomers被完成。测试了这些新化合物在各种不对称有机转化中的催化性能，并与第一代催化剂进行了比较。已经发现，新型催化剂可以在不使用有机溶剂的情况下，并且通过使用几乎化学计量的试剂，可以有效地催化盐水中的反应。因此，通过简单的提取就可以分离出产物，从而避免了以极高的收率，非对映选择性和对映选择性使用色谱法。
• Enantioselective Organocatalytic α-Alkylation of Ketones by SN1-Type Reaction of Alcohols
  作者：Maria Trifonidou、Christoforos G. Kokotos

  DOI：10.1002/ejoc.201101509

  日期：2012.3

  The enantioselective α-alkylation reaction of cyclic ketones is described. Our catalyst, based on a “privileged” pyrrolidine ring bearing a chiral thioxotetrahydropyrimidinone ring, is a highly reactive catalyst for cyclic ketones. When this catalyst was coupled with in situ generated carbocations derived from alcohols, the corresponding α-alkylated adducts were obtained in moderate to quantitative

  描述了环酮的对映选择性α-烷基化反应。我们的催化剂基于带有手性硫代四氢嘧啶酮环的“特权”吡咯烷环，是一种高反应性的环酮催化剂。当这种催化剂与原位生成的由醇衍生的碳阳离子偶联时，相应的 α-烷基化加合物以中等到定量的产率和低到高的对映选择性（高达 80% ee）获得。催化剂负载量可有效降低至 10%，这是文献中报道的此类有机催化转化的最低值。
• Kinetic Evidence for the Formation of Oxazolidinones in the Stereogenic Step of Proline-Catalyzed Reactions
  作者：Tanja Kanzian、Sami Lakhdar、Herbert Mayr

  DOI：10.1002/anie.201004344

  日期：2010.12.3

  Neighboring‐group participation: Anchimeric assistance of the carboxylate group accelerates the attack of the electrophiles at the double bond of the proline‐derived enamine A by a factor of about 50.

  邻近基团的参与：羧酸酯基团的邻位协助可将亲电体对脯氨酸衍生的烯胺A的双键的攻击加速约50倍。
• Functionalized Chiral Ionic Liquid Catalyzed Asymmetric SN1 α-Alkylation of Ketones and Aldehydes
  作者：Long Zhang、Lingyun Cui、Xin Li、Jiuyuan Li、Sanzhong Luo、Jin-Pei Cheng

  DOI：10.1002/ejoc.201000609

  日期：2010.9

  Pyrrolidine-derived functionalized chiral ionic liquids (FCILs) have been found to catalyze asymmetric S N 1 α-alkylations of ketones and aldehydes with up to 99 % yield, >99:1 dr and 87 % ee. The FCIL catalysts enable S N 1 α-alkylations of cyclic ketones, particularly of 3- and 4-substituted cyclohexanones with excellent diastereoselectivity and good enantioselectivity, featuring unprecedented desymmetrization

  已发现吡咯烷衍生的官能化手性离子液体 (FCIL) 可催化酮和醛的不对称 SN 1 α-烷基化反应，产率高达 99%，>99:1 dr 和 87% ee。FCIL 催化剂使环酮，特别是 3-和 4-取代环己酮的 SN 1 α-烷基化具有优异的非对映选择性和良好的对映选择性，为这些类型的不对称反应提供了前所未有的去对称化和动力学拆分过程。介绍了这项研究的全部细节以及提议的烯胺过渡态。
• Asymmetric S_N1 α-Alkylation of Cyclic Ketones Catalyzed by Functionalized Chiral Ionic Liquid (FCIL) Organocatalysts
  作者：Long Zhang、Lingyun Cui、Xin Li、Jiuyuan Li、Sanzhong Luo、Jin-Pei Cheng

  DOI：10.1002/chem.200902509

  日期：2010.2.15

  Ionic liquid works better: The first intermolecular asymmetric α‐alkylation of cyclic ketones was realized by using functionalized chiral ionic liquids as catalysts. The reaction proceeded with good to excellent yields and high ee. Highly stereoselective desymmetrization of 4‐substituted cyclohexanones with >99:1 d.r. and up to 87 % ee were achieved by using this protocol.

  离子液体效果更好：环状酮的第一个分子间不对称α-烷基化反应是通过使用功能化的手性离子液体作为催化剂来实现的。反应以良好至优异的产率和高ee进行。通过使用该协议，可以实现具有> 99：1 dr和高达87％ee的4-取代环己酮的高度立体选择性去对称化 。