N-benzyhydryl-(2-methylbenzylidene)-amine | 330455-48-6

• 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: N-benzyhydryl-(2-methylbenzylidene)-amine
• 英文别名: o-methylbenzaldehyde benzhydrylimine
• CAS: 330455-48-6
• 化学式: C₂₁H₁₉N
• 分子量: 285.389
• InChiKey: HOZILZFLRNSENW-CJLVFECKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  22.0
• 可旋转键数：
  4.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  12.36
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  反-1-甲氧基-3-(三甲基硅氧基)-1,3-丁二烯 、 N-benzyhydryl-(2-methylbenzylidene)-amine 在 ytterbium(III) triflate 作用下， 以 甲苯 为溶剂， 反应 24.0h， 以46%的产率得到1-benzhydryl-2,3-dihydro-2-o-tolylpyridin-4(1H)-one
  参考文献：
  名称：

  Regulation of Orthogonal Functions in a Dual Catalyst System. Subservient Role of a Nonchiral Lewis Acid in an Asymmetric Catalytic Heteroatom Diels−Alder Reaction

  摘要：

  A catalytic asymmetric heteroatom Diels-Alder reaction of unactivated imines with Danishefsky's diene is described which gives high asymmetric induction for N-benzhydryl imines derived from a variety of aldehydes. The catalyst is derived from B(OPh)(3) and the VAPOL ligand and gives good induction, but the reaction stalls and does not give high conversion (similar to 50%). It was found that in the presence of both the chiral catalyst and excess amounts of B(OPh)(3) the reaction proceeds to completion and gives high yields of the dihydropiperidinone product. Despite the presence of large quantities of the nonchiral Lewis acid B(OPh)(3), the asymmetric induction of the product remains constant (90% ee) as the amount of B(OPh)(3) is steadily increased and does not drop off until the ratio of B(OPh)(3) to VAPOL is 100:1 (82% ee). These observations are interpreted as involving highly separated and different activities for the chiral and nonchiral Lewis acids present in the reaction. Specifically, the excess B(OPh)(3) serves to bind to the product and release the chiral catalyst to turnover more starting material. The B(OPh)(3) does not compete in turning over the starting material, and a series of binding studies reveal that this is likely due to a combination of two factors. The binding studies reveal that the chiral catalyst binds to the starting imine 7 times more strongly than does B(OPh)(3). However, in order to explain the constant asymmetric induction observed despite the addition of increasing amounts of B(OPh)(3), the rate of the reaction of the imine complexed with the chiral catalyst must be at least 10 times faster than the reaction of the imine complexed with B(OPh)(3). Finally, a catalyst generated from BINOL and B(OPh)(3) does not show this phenomenon.

  DOI：

  10.1021/ja069019d
• 作为产物：
  描述：

  2-甲基苯甲醛 、 二苯甲胺 在 magnesium sulfate 作用下， 以 二氯甲烷 为溶剂， 反应 8.0h， 生成 N-benzyhydryl-(2-methylbenzylidene)-amine
  参考文献：
  名称：

  利用新型 Tropos 联苯二醇基配体进行 N-二苯甲基亚胺的不对称 Strecker 反应

  摘要：

  介绍了 N-arenesulfonyl-1,3-oxazolidinyl 取代的联苯二醇库的合成。一组两个中心中间体与易于获得的 N-芳烃磺酰氨基醇一起提供了种类繁多的 1,3-恶唑烷。这些在钛介导的 N-二苯甲基亚胺的 Strecker 型反应中用作手性原配体。在产物中的ee值和关于配体手性轴的非对映体比率之间建立相关性。配体中的那些取代基被证明导致对相关化合物中手性轴的一种非对映异构体的更高偏好，现在提供了最具选择性的配体。在 13 次筛选中的 8 次中发现了两种特权配体，可提供优异的结果。（© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008）

  DOI：

  10.1002/ejoc.200700763

文献信息

• Aziridinyl Vinyl Ketones from the Asymmetric Catalytic Aziridination Reaction
  作者：Yonghong Deng、Young Rok Lee、Cory A. Newman、William D. Wulff

  DOI：10.1002/ejoc.200601126

  日期：2007.5

  Under the aegis of boron Lewis acids, prepared from either the vanol or vapol ligand, vinyl aziridinyl ketones can be obtained with a high degree of asymmetric induction from the catalytic asymmetric aziridination reaction (AZ) of imines and vinyl diazomethyl ketones. The products have potential as synthons for five-carbon chiral amines. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany

  在由 vanol 或 vapol 配体制备的硼路易斯酸的支持下，可以通过亚胺和乙烯基重氮甲基酮的催化不对称氮丙啶化反应 (AZ) 的高度不对称诱导获得乙烯基氮丙啶酮。该产品具有作为五碳手性胺合成子的潜力。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
• A highly enantioselective Strecker reaction catalyzed by titanium-N-salicyl-β-aminoalcohol complexes
  作者：Vorawit Banphavichit、Woraluk Mansawat、Worawan Bhanthumnavin、Tirayut Vilaivan

  DOI：10.1016/j.tet.2004.07.097

  日期：2004.11

  evaluated as ligands for catalytic asymmetric Strecker reactions. N-Benzhydrylaldimines derived from aromatic and aliphatic aldehydes reacted with TMSCN in the presence of 10 mol% of Ti-1 complex to give the Strecker products in excellent yields and in up to >98% ee. The presence of a protic additive is essential to ensure good conversion and reaction rate. The reaction conditions are simple and the stereochemical

  合成了N-水杨基-β-氨基醇1并作为催化不对称Strecker反应的配体进行了评估。在10摩尔％的Ti- 1配合物的存在下，衍生自芳族和脂族醛的N-苯甲基乙二胺与TMSCN反应，以优异的收率和高达> 98％ee的浓度获得Strecker产品。质子添加剂的存在对于确保良好的转化率和反应速率至关重要。反应条件简单，并且根据配体的构型可以预测其立体化学结果，所述配体的两个对映体均易于合成。
• Enantioselective Strecker Reactions between Aldimines and Trimethylsilyl Cyanide Promoted by ChiralN,N′-Dioxides
  作者：Zhigang Jiao、Xiaoming Feng、Bo Liu、Fuxue Chen、Guolin Zhang、Yaozhong Jiang

  DOI：10.1002/ejoc.200300319

  日期：2003.10

  Axially chiral N,N'-dioxide Lewis base promoters have been developed and have for the first time been applied to the asymmetric synthesis of alpha-amino nitriles through cyanide addition to aldimines. The chiral 3,3'-dimethyl-2,2'-biquinoline N,N'-dioxide 2 exhibited high enantioselectivity for asymmetric Strecker reactions between N-benzhydrylimines and trimethylsilyl cyanide. In the presence of 1

  已开发出轴向手性 N,N'-二氧化物路易斯碱促进剂，并首次应用于通过向醛亚胺加成氰化物来不对称合成 α-氨基腈。手性 3,3'-二甲基-2,2'-双喹啉 N,N'-二氧化物 2 对 N-二苯甲基亚胺和三甲基甲硅烷基氰化物之间的不对称 Strecker 反应表现出高对映选择性。在 1 当量的情况下。对于手性促进剂 2，醛亚胺的氰基硅烷化提供了相应的 α-氨基腈，其 ee 值高达 95%。在某些产品的情况下，仅通过重结晶即可获得光学纯产品 (99% ee)。此外，促进剂2可以被回收和重复使用至少四次而没有任何对映选择性和反应性的损失。还讨论了对映选择性 Strecker 反应的推定机制。((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)。
• A Mild and Efficient Synthesis of 2,5-Disubstituted 2,3-Dihydro-4-pyridones Catalyzed by Yb(OTf)₃
  作者：Xiaoming Feng、Ke Cheng、Baiqing Zeng、Zhipeng Yu、Bo Gao

  DOI：10.1055/s-2005-864810

  日期：——

  A highly efficient aza-Diels-Alder reaction of trans-1-methoxy-2-methyl-3-trimethylsiloxybuta-1,3-diene with N-benz­hydryl imines was catalyzed by Yb(OTf)3 in toluene at room temperature to give corresponding 2,5-disubstituted 2,3-dihydro-4-pyridones in high yields. Three-component reactions of diene with aldehydes and amines were also performed smoothly to afford the desired cycloadducts under solvent-free condition in 51-86% yields.

  在室温下，Yb(OTf)3 在甲苯中催化了反式-1-甲氧基-2-甲基-3-三甲基硅氧基丁-1,3-二烯与 N-二苯基亚胺的高效杂氮-Diels-Alder 反应，得到了相应的 2,5-二取代 2,3-二氢-4-吡啶酮，收率很高。二烯与醛和胺的三组分反应也在无溶剂条件下顺利进行，以 51-86% 的收率得到了所需的环加载产物。
• Catalytic Asymmetric Aziridination with Arylborate Catalysts Derived from VAPOL and VANOL Ligands
  作者：Jon C. Antilla、William D. Wulff

  DOI：10.1002/1521-3773(20001215)39:24<4518::aid-anie4518>3.0.co;2-j

  日期：2000.12.15