(E)-N-(2-bromobenzylidene)-P,P-diphenylphosphinic amide | 252377-09-6

• 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: (E)-N-(2-bromobenzylidene)-P,P-diphenylphosphinic amide
• 英文别名: (E)-1-(2-bromophenyl)-N-diphenylphosphorylmethanimine
• CAS: 252377-09-6
• 化学式: C₁₉H₁₅BrNOP
• 分子量: 384.212
• InChiKey: PGRDFJJXHAVIKL-RCCKNPSSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  29.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (E)-N-(2-bromobenzylidene)-P,P-diphenylphosphinic amide 、 (1R,2S,4S)-(+)-(N-bromoacetyl)bornane-10,2-sultam 在 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 反应 4.5h， 以67%的产率得到trans-(1R,2S,4S)-N-[(1'-diphenylphosphinyl-(3'R)-3'-(2-bromophenyl)-(2'S)-2'-aziridinyl)carbonyl]bornane-10,2-sultam
  参考文献：
  名称：

  Inverted Diastereoselectivity in Asymmetric Aziridine Synthesis via Aza-Darzens Reaction of (2S)-N-Bromoacyl Camphorsultam

  摘要：

  [GRAGHICS]The aza-Darzens reaction of the chiral enolate derived from (2S) bromoacetyl camphor sultam (1) with certain C-3-substituted N-diphenylphosphinyl imines gives mixtures of trans- and cis-aziridines. In some cases, only trans isomers are observed. A steric repulsion between the enolate halogen atom and this C-3-substituent is invoked to rationalize these observations.

  DOI：

  10.1021/ol990874u
• 作为产物：
  描述：

  二苯基磷酰胺 在 N-(chlorosulfinyl)imidazole 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 22.0h， 生成 (E)-N-(2-bromobenzylidene)-P,P-diphenylphosphinic amide
  参考文献：
  名称：

  Synthesis of N-Diphenylphosphinoylimines Using the Kresze Reaction

  摘要：

  The synthesis of N-diphenylphosphinoylimines involving the treatment of aldehydes with PP-diphenyl N-sulfinylphosphoramidate (Ph2P(O)NSO) is described. The reagent is prepared from PP-diplienylphosphinic amide, thionyl chloride, and imidazole.

  DOI：

  10.1021/jo051491e

文献信息

• Enantioselective synthesis of diaryl aziridines using tetrahydrothiophene-based chiral sulfides as organocatalysts
  作者：Meng-Ting Huang、Hsin-Yi Wu、Rong-Jie Chein

  DOI：10.1039/c3cc47550f

  日期：——

  This work describes catalytic and asymmetric aziridinations (15 examples, 95-98% ee) of benzyl bromide and imines via the imino Corey-Chaykovsky reaction using (thiolan-2-yl)diarylmethanol benzyl ether as an organocatalyst. The catalyst and analogues thereof were prepared through an expeditious and efficient synthetic route featuring a double nucleophilic substitution and Shi epoxidation as key steps

  这项工作描述了使用（thiolan-2-yl）diarylmethanol苄基醚作为有机催化剂通过亚氨基Corey-Chaykovsky反应进行的苄基溴和亚胺的催化和不对称叠氮化（15例，95-98％ee）。通过快速有效的合成途径制备催化剂及其类似物，所述合成途径以双亲核取代和Shi环氧化为关键步骤。
• [EN] SIMPLE ORGANIC MOLECULES AS CATALYSTS FOR PRACTICAL AND EFFICIENT ENANTIOSELECTIVE SYNTHESIS OF AMINES AND ALCOHOLS<br/>[FR] MOLÉCULES ORGANIQUES SIMPLES EN TANT QUE CATALYSEURS POUR LA SYNTHÈSE ÉNANTIOSÉLECTIVE PRATIQUE ET EFFICACE D'AMINES ET D'ALCOOLS
  申请人：TRUSTEES BOSTON COLLEGE

  公开号：WO2013131043A1

  公开（公告）日：2013-09-06

  The present invention provides organic molecules and methods thereof for reactions between organoboron reagents and double bonds, such as imines or carbonyls, to stereoselectively provide chiral products including amines and alcohols, entities useful for the preparation of biologically active molecules.

  本发明提供了有机分子及其方法，用于有机硼试剂与双键（如亚胺或羰基）之间的反应，以立体选择性地提供手性产物，包括胺和醇等实体，用于制备具有生物活性的分子。
• The Catalytic Asymmetric Addition of Diethylzinc toN-(Diphenylphosphinoyl) Imines Catalyzed by Cu(OTf)2-ChiralN-(Binaphthyl-2-yl)thiophosphoramide Ligands
  作者：Min Shi、Chun-Jiang Wang

  DOI：10.1002/adsc.200303041

  日期：2003.8

  Chiral N-(binaphthyl-2-yl)thiophosphoramide L7 [O,O-diethyl 2′-(ethylamino)-1,1′-binaphthyl-2-ylamidothiophosphate] prepared from the reaction of diethyl chlorothiophosphate with (R)-(+)-N-ethyl-1,1′-binaphthyl-2,2′-diamine was used as a catalytic chiral ligand in the first Cu(OTf)2-promoted catalytic asymmetric addition of diethylzinc to N-(diphenylphosphinoyl) imines in which ~85% ee can be realized

  手性ñ - （联萘-2-基）硫代磷酰胺L7 [ O，O-二乙基-2' - （乙基氨基）-1,1'-联萘-2- ylamidothiophosphate]从二氯代硫代磷酸酯与反应制备（[R ）- （+ ）-N-乙基-1,1'-联萘-2,2'-二胺在第一个Cu（OTf）2促进的二乙基锌向N-（二苯基膦酰基）亚胺的催化不对称加成中用作催化手性配体可以实现〜85％ee。
• Cooperative, Highly Enantioselective Phosphinothiourea Catalysis of Imine−Allene [3 + 2] Cycloadditions
  作者：Yuan-Qing Fang、Eric N. Jacobsen

  DOI：10.1021/ja801344w

  日期：2008.4.1

  A new family of phosphinthiourea catalysts was developed for the highly enantioselective synthesis of 2-aryl-2,5-hydropyrroles via a [3 + 2] cycloaddition of an electron-deficient allene with aryl and heteroaryl diphenylphosphinoylimines. The presence of both H(2)O and Et(3)N as additives was found to be important for achieving optimal rates. Dual activation of both nucleophile and electrophile by the bifunctional catalyst is invoked to account for the observed high reactivity and enantioselectivity.
• Inverted Diastereoselectivity in Asymmetric Aziridine Synthesis via <i>Aza</i>-Darzens Reaction of (2<i>S</i>)-<i>N</i>-Bromoacyl Camphorsultam
  作者：Andrew B. McLaren、J. B. Sweeney

  DOI：10.1021/ol990874u

  日期：1999.11.1

  [GRAGHICS]The aza-Darzens reaction of the chiral enolate derived from (2S) bromoacetyl camphor sultam (1) with certain C-3-substituted N-diphenylphosphinyl imines gives mixtures of trans- and cis-aziridines. In some cases, only trans isomers are observed. A steric repulsion between the enolate halogen atom and this C-3-substituent is invoked to rationalize these observations.