(R)-(+)-N-[1-(4-methylphenyl)propyl]-P,P-diphenylphosphinic amide

• 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: (R)-(+)-N-[1-(4-methylphenyl)propyl]-P,P-diphenylphosphinic amide
• 英文别名: N-[(1R)-1-(4-methylphenyl)propyl]-P,P-diphenylphosphinic amide；(R)-N-[1-(4-methylphenyl)propyl]-P,P-diphenylphosphinoylamide；(+)-N-[1-(4-methylphenyl)propyl]-P,P-diphenylphosphinamide；N-[1-(4'-methylphenyl)propyl]-P,P-diphenylphosphinoylamide；N-[1-(4-methylphenyl)propyl]-P,P-diphenylphosphinoylamide；(R)-(+)-N-(1-p-tolylpropyl)-P,P-diphenylphosphinoylamide；(1R)-N-diphenylphosphoryl-1-(4-methylphenyl)propan-1-amine
• 化学式: C₂₂H₂₄NOP
• 分子量: 349.412
• InChiKey: DDPJLTWMDNAGRN-JOCHJYFZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  25
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  diethylzinc 、 N-(4-methylbenzylidene)-P,P-diphenylphosphinic amide 在 (1S,2R,4R)-7,7-dimethyl-1-morpholin-4-yl-bicyclo[2.2.1]heptan-2-ol 作用下， 以 甲苯 、 正己烷 为溶剂， 反应 51.17h， 以95%的产率得到(R)-(+)-N-[1-(4-methylphenyl)propyl]-P,P-diphenylphosphinic amide
  参考文献：
  名称：

  樟脑衍生的手性β-氨基醇介导的二烷基锌与芳香亚胺的对映选择性加成

  摘要：

  在1或2介导的N-（二苯基膦酰基）亚胺中对二乙基锌或二甲基锌的对映选择性加成（70-97％）和对映选择性（85-98％ee）可以实现。当反应在1.8当量甲醇的存在下进行时，亚胺的甲基化或乙基化反应可以将1或2 a的催化负载降低至10 mol％，从而获得高收率和对映选择性（79-96％）。ñ单取代的氨基醇比他们更高的诱导对映选择性ñ，ñ在我们的催化体系双取代同类。

  DOI：

  10.1002/asia.201403240

文献信息

• Catalytic Enantioselective Addition of Dialkylzinc to <i>N</i>-Diphenylphosphinoylimines. A Practical Synthesis of α-Chiral Amines
  作者：Alessandro A. Boezio、André B. Charette

  DOI：10.1021/ja027673x

  日期：2003.2.19

  The enantioselective addition of dialkylzinc reagents to N-diphenylphosphinoylimines derived from aryl-, furyl-, and cyclopropylaldehydes is efficiently catalyzed by a copper(II) triflate/(R,R)-MeDUPHOS complex. The yields are high (51-98%), and the enantiomeric excesses vary from 85 to 96%. This route provides a practical route to alpha-chiral amines.

  二烷基锌试剂与芳基-、呋喃基-和环丙醛衍生的 N-二苯基膦亚胺的对映选择性加成是由三氟甲磺酸铜 (II)/(R,R)-MeDUPHOS 复合物有效催化的。产率高 (51-98%)，对映体过量在 85% 至 96% 之间变化。该路线提供了获得 α-手性胺的实用路线。
• Modification of (1R,2S)-1,2-Diphenyl-2-aminoethanol for the Highly Enantioselective, Asymmetric Alkylation ofN-Diphenylphosphinoyl Arylimines with Dialkylzinc
  作者：Hai-Le Zhang、Fan Jiang、Xiao-Mei Zhang、Xin Cui、Liu-Zhu Gong、Ai-Qiao Mi、Yao-Zhong Jiang、Yun-Dong Wu

  DOI：10.1002/chem.200305418

  日期：2004.3.19

  Experimental studies on the modification of (1R,2S)-1,2-diphenyl-2-aminoethanol, which is used to promote the alkylation of N-diphenylphosphinoyl benzalimine with diethylzinc, revealed that N-monosubstituted amino alcohols exhibited higher enantioselectivities than their N,N-disubstituted counterparts and imino alcohols. Application of the optimal chiral ligand 3c to activate the reaction of N-diphenylphosphinoyl

  对用于促进N-二苯基膦酰基苯扎明与二乙基锌烷基化的（1R，2S）-1,2-二苯基-2-氨基乙醇的改性实验研究表明，N-单取代氨基醇的对映选择性高于N ，N-二取代对应物和亚氨基醇。最佳手性配体3c的应用可激活N-二苯基膦酰基芳基丙氨酸与二乙基锌和二丁基锌的反应，可产生高达98％ee的出色对映异构体选择性。通过对几种模型反应的过渡结构进行密度泛函计算（B3LYP / 6-31G *），揭示了实验观察到的对映选择性的起源。
• METHOD OF ENANTIOSELECTIVE ADDITION TO IMINES
  申请人：UANG Biing-Jiun

  公开号：US20120004441A1

  公开（公告）日：2012-01-05

  The present invention relates to a method of enantioselective addition to imines, including: reacting R 3 CH═NY with R 4 ZnR 5 in the presence of a compound represented by the following formula (I), in which Y, R 1 , R 2 , R 3 , R 4 and R 5 are defined the same as the specification. Accordingly, the present invention can prepare secondary amines in high yields and enantiomeric excess by the above-mentioned method.

  本发明涉及一种对亚胺进行对映选择性加成的方法，包括：在以下式(I)所代表的化合物存在下，将R3CH═NY与R4ZnR5反应，其中Y、R1、R2、R3、R4和R5的定义与规范相同。因此，本发明可以通过上述方法高产率和对映过量地制备二级胺。
• Asymmetric Synthesis of N-(Diphenylphosphinyl)amines Promoted by Chiral Carbosilane Dendritic Ligands in The Enantioselective Addition of Dialkylzinc Compounds to N-(Diphenylphosphinyl)imines
  作者：Itaru Sato、Kenji Hosoi、Ryo Kodaka、Kenso Soai

  DOI：10.1002/1099-0690(200209)2002:18<3115::aid-ejoc3115>3.0.co;2-9

  日期：2002.9

  The enantioselective addition of dialkylzinc compounds to N-(diphenylphosphinyl)imines by using chiral dendrimers with flexible carbosilane backbones gives enantiomerically enriched N-(diphenylphosphinyl)amines with up to 92% ee. (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

  通过使用具有柔性碳硅烷主链的手性树枝状聚合物将二烷基锌化合物对映选择性加成到 N-（二苯基膦基）亚胺中，得到对映异构富集的 N-（二苯基膦基）胺，其 ee 高达 92%。(© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)
• Asymmetric synthesis of N-diphenylphosphinoylamines by solvent-free enantioselective addition of dialkylzincs to N-diphenylphosphinoylimines
  作者：Itaru Sato、Ryo Kodaka、Kenso Soai

  DOI：10.1039/b106775n

  日期：2001.11.15

  Solvent-free enantioselective addition of dialkylzincs to N-diphenylphosphinoylimines in the presence of chiral 2-morpholino-1-phenylpropan-1-ol affords N-diphenylphosphinoylamines with up to 97% ee. The reaction in the solvent-free system is faster than in organic solvents.

  在手性2-吗啉代-1-苯基丙-1-醇的存在下，无溶剂条件下对N-二苯基膦酰亚胺进行二烷基锌的选择性不对称加成，可以得到最高达97% ee的N-二苯基膦酰胺。与有机溶剂相比，无溶剂体系中的反应速度更快。