N-benzyhydryl-(1-naphthalidene)-amine | 330455-51-1

• 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-(1-naphthalidene)-amine
• 英文别名: (E)-N-(naphthalen-1-ylmethylene)-1,1-diphenylmethanamine
• CAS: 330455-51-1
• 化学式: C₂₄H₁₉N
• 分子量: 321.422
• InChiKey: DWNIZKXNTWYTAJ-XIEYBQDHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.05
• 重原子数：
  25.0
• 可旋转键数：
  4.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.04
• 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-(1-naphthalidene)-amine 在 ytterbium(III) triflate 作用下， 以 甲苯 为溶剂， 反应 24.0h， 以52%的产率得到1-benzhydryl-2,3-dihydro-2-(naphthalen-1-yl)pyridin-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：

  1-萘甲醛 、 二苯甲胺 以 二氯甲烷 为溶剂， 反应 48.0h， 以75%的产率得到N-benzyhydryl-(1-naphthalidene)-amine
  参考文献：
  名称：

  Si-B键的激活：铜催化的亲核硅与亚胺的加成反应

  摘要：

  通过铜催化的过渡金属化对Si-B键的激活迅速发展为一种生成Cu-Si试剂的实用方法。这些硅亲核试剂干净地添加到醛衍生的亚胺亲电试剂中，从而在质子介质中形成α-甲硅烷基化胺，并且未观察到中间阴离子的碳-氮布鲁克型重排。除了亚胺氮原子上的吸电子基团（例如SO 2 Tol和P（O）Ph 2）外，还可以耐受先前精密的氮取代基，例如苯基或二苯甲基。相同的协议还允许史无前例地添加代表酮的亚胺。

  DOI：

  10.1021/ol200509c

文献信息

• Asymmetric Strecker Reaction ofN-Benzhydrylimines Utilising New Tropos Biphenyldiol-Based Ligands
  作者：Stefan Wünnemann、Roland Fröhlich、Dieter Hoppe

  DOI：10.1002/ejoc.200700763

  日期：2008.2

  intermediates together with easily accessible N-arenesulfonylamino alcohols furnish a broad variety of 1,3-oxazolidines. These are applied as chiral tropos ligands in a titanium-mediated Strecker-type reaction of N-benzhydrylimines. A correlation between the ee values in the product and the diastereomeric ratio concerning the chiral axis of the ligand is made. Those substituents in the ligand which proved

  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）
• Enantioselective Synthesis of α-Amino Nitriles from <i>N</i>-Benzhydryl Imines and HCN with a Chiral Bicyclic Guanidine as Catalyst
  作者：E. J. Corey、Michael J. Grogan

  DOI：10.1021/ol990623l

  日期：1999.7.1

  [formula: see text] A novel catalytic enantioselective Strecker synthesis of chiral alpha-amino nitriles and alpha-amino acids is described and analyzed with regard to the possible mechanistic basis for stereoselectivity. Key features of the enantioselective process include (1) the use of the chiral bicyclic guanidine 1 as catalyst and (2) the use of the N-benzhydryl substituent on the imine substrate

  描述和分析了手性α-氨基腈和α-氨基酸的新型催化对映选择性Strecker合成方法，并分析了立体选择性的可能机理。对映选择性方法的关键特征包括（1）使用手性双环胍1作为催化剂和（2）在亚胺底物上使用N-苯甲酰基取代基。
• 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。
• Facile Synthesis of Aziridines from Imines and Diazoesters or Aldehydes, Amines, and Diazoesters Using a Catalytic Amount of Lanthanide Triflate
  作者：Satoshi Nagayama、Shu Kobayashi

  DOI：10.1246/cl.1998.685

  日期：1998.7

  In the presence of a catalytic amount of lanthanide triflate (Ln(OTf)3), imines reacted with ethyl diazoester in hexane at room temperature to afford the corresponding aziridines in high yields with high diastereoselectivities. Based on these reactions, three-component reactions of various types of aldehydes, an amine, and ethyl diazoester have been developed to provide a general efficient route to

  在催化量的镧系元素三氟甲磺酸盐 (Ln(OTf)3) 存在下，亚胺与重氮乙酯在己烷中在室温下反应，以高产率和高非对映选择性得到相应的氮丙啶。基于这些反应，已开发出各种醛、胺和乙基重氮酯的三组分反应，为获得氮丙啶衍生物的通用有效途径提供了途径。
• Chirally and Chemically Reversible Strecker Reaction
  作者：Yutaro Machida、Yudai Tanaka、Yuya Masuda、Aya Kimura、Tsuneomi Kawasaki

  DOI：10.1039/d3sc00359k

  日期：——

  In the pursuit of a credible mechanism for the abiotic synthesis of α-amino acids, solid-state asymmetric Strecker/retro-Strecker reactions have been demonstrated. Asymmetric addition of cyanide to enantiomorphic crystals of achiral imines proceeded to produce enantioenriched aminonitriles. Moreover, dehydrocyanation of enantioenriched aminonitriles gave chiral crystals of achiral imines stereoselectively

  在寻求 α-氨基酸非生物合成的可靠机制时，已经证明了固态不对称 Strecker/retro-Strecker 反应。将氰化物不对称加成到非手性亚胺的对映体晶体中，可生成富含对映体的氨基腈。此外，对映体富集的氨基腈的脱氢氰化立体选择性地得到非手性亚胺的手性晶体。据我们所知，我们首次发现合成中间体亚胺和氨基腈在反应序列（包括 HCN 加成和消除）中的立体转化。因此，可逆的Strecker反应有望成为手性起源研究的热点。