N-piperonylmethylidene-P,P-diphenylphosphinamide

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并间二氧杂环戊烯类
• 英文名称: N-piperonylmethylidene-P,P-diphenylphosphinamide
• 英文别名: (E)-1-(1,3-benzodioxol-5-yl)-N-diphenylphosphorylmethanimine
• 化学式: C₂₀H₁₆NO₃P
• 分子量: 349.326
• InChiKey: YRHIKZFEFIEWOZ-KGENOOAVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  25
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  47.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  diethylzinc 、 N-piperonylmethylidene-P,P-diphenylphosphinamide 在 copper(II) bis(trifluoromethanesulfonate) 、 1,2-双[(2R,5R)-2,5-二甲基磷]一氧化苯 作用下， 以 甲苯 为溶剂， 反应 40.5h， 以93%的产率得到(S)-N-{1-[3,4-(methylenedioxy)phenyl]propyl}-P,P-diphenylphosphinamide
  参考文献：
  名称：

  使用新型双（膦）一氧化物手性配体不对称催化合成 α-手性胺

  摘要：

  我们已经证明 Me-DuPHOS 一氧化 (BozPHOS) 在铜催化下将二烷基锌加成到 N-膦亚胺中是一种非常有效的配体，提供了获得 α-手性胺的途径。新配体对于添加反应性较低的二甲基锌特别有效。该方法的主要优点是收率高、底物范围广、对映选择性高、催化剂负载量低（3 mol%）。

  DOI：

  10.1021/ja038291+

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。
• Evaluation of Chiral Oxazolines for the Highly Enantioselective Diethylzinc Addition to <i>N</i>-(Diphenylphosphinoyl) Imines
  作者：Xiao-Mei Zhang、Hai-Le Zhang、Wen-Qing Lin、Liu-Zhu Gong、Ai-Qiao Mi、Xin Cui、Yao-Zhong Jiang、Kai-Bei Yu

  DOI：10.1021/jo0268862

  日期：2003.5.1

  generally offered higher enantioselectivity than those containing an ortho-substituted phenyl. The X-ray structures of 4f and 4j, in combination with the proposed transition state, preliminarily explained why oxazolines with a para- or meta-substituent on the phenyl group gave higher enantioselectivities than those bearing an ortho-substituent. This successful example using chiral oxazolines to promote

  根据在β-氨基醇中引入结构刚性和构象受限的骨架有利于亚胺的对映选择性二乙基锌的原理，一系列手性恶唑啉已被设计并从市售方便地制备（1S除二苯基膦酰基亚胺外，将（2S）-2-氨基-1-苯基丙烷-1，3-二醇用于二乙基锌中，得到68-84％的高产率和90-95％的优异ee值。通过与恶唑啉中的羟基键合的碳的手性来控制产物的构型。带有对位或间位取代的苯基的恶唑啉通常比含有邻位取代的苯基的那些具有更高的对映选择性。4f和4j的X射线结构，结合所提出的过渡态，初步解释了为什么在苯基上具有对位或间位取代基的恶唑啉比具有邻位取代基的恶唑啉具有更高的对映选择性。使用手性恶唑啉促进标题反应的成功实例表明，含有恶唑啉环部分的许多手性化合物具有开发出促进除N-（二苯基膦酰基）亚胺以外的高对映选择性二烷基锌的潜力。
• Enantioselective addition of diethylzinc to N-diphenylphosphinoylimines employing N,N-dialkyl-1,2-diphenyl-2-aminoethanols as chiral ligands
  作者：Xiaomei Zhang、Liuzhu Gong、Aiqiao Mi、Xin Cui、Yaozhong Jiang、Michael C. K. Choi、Albert S. C. Chan

  DOI：10.1016/s0040-4039(01)01273-4

  日期：2001.9

  By fine-tuning the substituents on the nitrogen of (1S,2R) and (1R,2S)-1,2-diphenyl-2-aminoethanols, a chiral ligand 2b was obtained, which showed excellent enantioselectivity, with up to 94% e.e, for the asymmetric addition of diethylzinc to N-diphenylphosphinoylimines 1. In one example, the optically active amide 3c was converted into a new amine 5 with 98% e.e. by a reaction sequence involving Suzuki coupling and hydrolysis without racemization. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Novel chiral copper complexes of N,P-ferrocenyl ligands with central and planar chirality as efficient catalyst for asymmetric addition of diethylzinc to imines
  作者：Min-Can Wang、Lan-Tao Liu、Yuan-Zhao Hua、Jun-Song Zhang、Yan-Yan Shi、De-Kun Wang

  DOI：10.1016/j.tetasy.2005.06.005

  日期：2005.8

  A new type of chiral copper complexes of N,P-ferrocenyl ligands with central and planar chirality as efficient catalyst was applied to the enantioselective addition of diethylzinc to N-diphenylphosphinoylimines. The (R)- and (s)-enantiomers of the addition reaction were obtained for this transformation. In the presence of 6 mol % of bidentate ligand 1 and 12 mol % of Cu(OTf)(2), the asymmetric addition process affords N-diphenylphosphinoylamides in up to 97% ee and 95% yields. (c) 2005 Elsevier Ltd. All rights reserved.