(R)-(+)-N-[1-(4-bromophenyl)propyl]-P,P-diphenylphosphinic amide | 374777-18-1

• 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: (R)-(+)-N-[1-(4-bromophenyl)propyl]-P,P-diphenylphosphinic amide
• 英文别名: (R)-(+)-N-[1-(4-bromophenyl)propyl]-P,P-diphenylphosphinoylamide；N-[(1R)-1-(4-bromophenyl)propyl]-P,P-diphenylphosphinic amide；(R)-N-(1-p-bromophenylpropyl)-P,P-diphenylphosphinoylamide；N-[1-(4-bromophenyl)propyl]-P,P-diphenylphosphinoylamide；N-[1-(4-broomophenyl)propyl]-P,P-diphenylphosphinamide；(1R)-1-(4-bromophenyl)-N-diphenylphosphorylpropan-1-amine
• CAS: 374777-18-1
• 化学式: C₂₁H₂₁BrNOP
• 分子量: 414.282
• InChiKey: XJQVIRWVOVEHJK-OAQYLSRUSA-N

物化性质

• 沸点：
  524.2±52.0 °C(Predicted)
• 密度：
  1.35±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  25
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (R)-(+)-N-[1-(4-bromophenyl)propyl]-P,P-diphenylphosphinic amide 在 oxonium 作用下， 生成 (R)-1-(p-bromophenyl)propan-1-amine
  参考文献：
  名称：

  Enantioselective addition of diethylzinc to N-diphenylphosphinoylimines employing N,N-dialkyl-1,2-diphenyl-2-aminoethanols as chiral ligands

  摘要：

  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.

  DOI：

  10.1016/s0040-4039(01)01273-4
• 作为产物：
  描述：

  (E)-N-(4-bromobenzylidene)-P,P-diphenylphosphinic amide 、 alkaline earth salt of/the/ methylsulfuric acid 在 (1R,2S)-2-(benzyl(methyl)amino)-1,2-diphenylethanol 作用下， 以 正己烷 、 甲苯 为溶剂， 反应 48.0h， 生成 (R)-(+)-N-[1-(4-bromophenyl)propyl]-P,P-diphenylphosphinic amide
  参考文献：
  名称：

  Enantioselective addition of diethylzinc to N-diphenylphosphinoylimines employing N,N-dialkyl-1,2-diphenyl-2-aminoethanols as chiral ligands

  摘要：

  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.

  DOI：

  10.1016/s0040-4039(01)01273-4

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。
• Asymmetric Addition of Diethylzinc to Diphenylphosphinoyl-Imines Catalyzed by Copper(II) Trifluoromethanesulfonate-Chiral (2′-Ethylamino-[1,1′]binaphthalenyl-2-yl)-thiophosphoramidic AcidO,O′-Diaryl Ester Ligands
  作者：Min Shi、Zhi-Yu Lei、Qin Xu

  DOI：10.1002/adsc.200606128

  日期：2006.10

  The chiral binaphthylthiophosphoramide L1 prepared from the reaction of O,O-diphenyl chlorothiophosphate with (R)-(+)-N-ethyl-1,1′-binaphthyl-2,2′-diamine was used as a catalytic chiral ligand in the copper(II) trifluoromethanesulfonate-promoted asymmetric addition of diethylzinc to diphenylphosphinoyl-imines to give the corresponding adducts in 90–98 % ee and good yields under mild conditions.

  手性binaphthylthiophosphoramide L1从反应制备O，O-二苯基磷酰氯与（[R ）- （+） - ñ -乙基- 1,1'-联萘-2,2'-二胺用作催化手性配体由三氟甲磺酸铜（II）促进的二乙基膦酸向二苯基膦酰基亚胺的不对称加成反应，得到相应的加合物，收率90-98％ee，在温和条件下收率良好。
• Catalytic asymmetric diethylzinc addition to diphenylphosphionyl imines using chiral tert-butanesulfinylphosphine ligands
  作者：Junmin Chen、Dong Li、Haifeng Ma、Linfeng Cun、Jin Zhu、Jingen Deng、Jian Liao

  DOI：10.1016/j.tetlet.2008.09.111

  日期：2008.11

  A class of novel chiral tert-butanesulfinylphosphine ligands were designed and synthesized by a concise two-step route with high yields. High activities and enantioselectivities (up to 94% ee) were achieved when using them in catalytic asymmetric diethylzinc addition to diphenylphosphionyl imines.

  通过简洁的两步法设计并合成了高收率的一类新型手性叔丁烷亚磺酰基膦配体。当将它们用于二苯基膦酰亚胺的催化不对称二乙基锌中时，可实现高活性和对映选择性（高达94％ee）。
• 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。
• The first use of chiral oxazoline ligands in the highly enantioselective diethylzinc addition to diphenylphosphinoyl imines
  作者：Xiaomei Zhang、Wenqing Lin、Liuzhu Gong、Aiqiao Mi、Xin Cui、Yaozhong Jiang、Michael C.K Choi、Albert S.C Chan

  DOI：10.1016/s0040-4039(02)00014-x

  日期：2002.2

  A series of chiral oxazolines, which had been conveniently prepared from commercially available (1S,2S)-2-amino-1-phenylpropane-1,3-diol, was applied in the diethylzinc addition to diphenylphosphinoyl imines to give high yields of 68–84% and excellent e.e. values of 90–93%.

  一系列手性恶唑啉是由市售（1 S，2 S）-2-氨基-1-苯基丙烷-1,3-二醇方便地制备的，将其用于二乙基膦酸的二乙基锌加成反应中，可获得高收率的手性恶唑啉。 68–84％，出色的ee值达到90–93％。