methyl (E)-3-(triphenylphosphoranylideneamino)but-2-enoate | 81777-30-2

• 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: methyl (E)-3-(triphenylphosphoranylideneamino)but-2-enoate
• 英文别名: 1,1,1-Triphenyl-3-methyl-4-(methoxycarbonyl)-2-aza-1λ⁵-phosphabuta-1,3-diene；methyl (E)-3-[(triphenyl-lambda5-phosphanylidene)amino]but-2-enoate；methyl (E)-3-[(triphenyl-λ5-phosphanylidene)amino]but-2-enoate
• CAS: 81777-30-2
• 化学式: C₂₃H₂₂NO₂P
• 分子量: 375.407
• InChiKey: NIMMJNPSXAUXOZ-VHEBQXMUSA-N

物化性质

• 熔点：
  146-149 °C
• 沸点：
  508.8±52.0 °C(Predicted)
• 密度：
  1.09±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  27
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.09
• 拓扑面积：
  38.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl (E)-3-(triphenylphosphoranylideneamino)but-2-enoate 在 四丁基氟化铵 作用下， 以 四氢呋喃 、 1,2-二氯乙烷 、 甲苯 为溶剂， 反应 9.0h， 生成 7-hydroxymethyl-1-(4-methoxy-benzylamino)-3-methyl-4a,5,6,7-tetrahydro-pyrrolo[1,2-c]pyrimidine-4-carboxylic acid methyl ester
  参考文献：
  名称：

  乙烯基碳二亚胺与 N-烷基亚胺的非对映选择性 [4+2] 环化。Batzelladine 生物碱的不对称合成途径

  摘要：

  已经开发出乙烯基碳二亚胺与手性 N-烷基亚胺的非对映选择性 [4+2] 环化，以获取巴泽拉定生物碱的立体化学丰富的三环核心。其在 batzelladine D 的不对称合成中的应用允许使用长程、定向氢化和立体选择性分子内碘胺化作为额外的关键步骤，以在具有出色立体控制的天然产物中建立剩余的立体中心。

  DOI：

  10.1021/ja0519029
• 作为产物：
  描述：

  methyl erythro-3-azido-2-iodo-butanoate 在 三乙烯二胺 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 25.0h， 生成 methyl (E)-3-(triphenylphosphoranylideneamino)but-2-enoate
  参考文献：
  名称：

  Cambie, Richard C.; Jurlina, Jeffrey L.; Rutledge, Peter S., Journal of the Chemical Society. Perkin transactions I, 1982, p. 327 - 334

  摘要：

  DOI：

文献信息

• Total Synthesis of (+)-Batzelladine A and (−)-Batzelladine D via [4 + 2]-Annulation of Vinyl Carbodiimides with <i>N</i>-Alkyl Imines
  作者：Michael A. Arnold、Kenneth A. Day、Sergio G. Durón、David Y. Gin

  DOI：10.1021/ja063860+

  日期：2006.10.1

  this strategy, together with additional key steps such as long-range directed hydrogenation and diastereoselective intramolecular iodo-amination, led to highly convergent total syntheses of (-)-batzelladine D and (+)-batzelladine A with excellent stereocontrol.

  已经开发出乙烯基碳二亚胺与手性 N-烷基亚胺的非对映选择性 [4 + 2]-环化，以获取 batzelladine 生物碱的立体化学丰富的多环胍核。该策略的应用，连同其他关键步骤，如远程定向氢化和非对映选择性分子内碘胺化，导致 (-)-batzelladine D 和 (+)-batzelladine A 的高度收敛全合成具有出色的立体控制。
• Regioselective synthesis of pyridines and dihydropyridines derived from β-amino acids and aminophosphonates by reaction of N-vinylic phosphazenes with α,β-unsaturated ketones
  作者：Francisco Palacios、Esther Herrán、Gloria Rubiales、Concepción Alonso

  DOI：10.1016/j.tet.2007.03.146

  日期：2007.6

  Reaction of N-vinylic phosphazenes with α,β-unsaturated ketones leads to the formation of pyridines derived from β-amino acids in a regioselective fashion. The use of functionalized enones derived from α-acylstyryl-carboxylates or -phosphonates affords biologically active asymmetrical and symmetrical dihydropyridines substituted with carboxylate or phosphonate groups including nitrendipine, felodipine

  的反应Ñ与α-vinylic磷腈，β不饱和酮导致吡啶的形成从β氨基酸在一个区域选择性的方式得到。使用衍生自α-酰基苯乙烯基-羧酸酯或-膦酸酯的官能化烯酮提供了被羧酸酯或膦酸酯基团取代的生物活性不对称和对称二氢吡啶，包括硝苯地平，非洛地平，MRS 1097和依诺地平类似物。
• Synthesis and Reactivity of Electron-Poor 2-Azadienes. [4 + 2] Cycloaddition Reactions with Alkenes and Enamines
  作者：Francisco Palacios、Itziar Perez de Heredia、Gloria Rubiales

  DOI：10.1021/jo00113a017

  日期：1995.4

  Electron deficient 2-azadienes derived from beta-amino acids 3 are obtained by aza-Wittig reaction of N-vinylic phosphazenes 4 with carbonyl compounds. Inverse electron demand Diels-Alder reaction of azadienes 3 with trans-cyclooctene 7 and cis,trans-cyclooctadiene 8 leads to the formation of trans-cycloalkanotetrahydropyridines 10. Heterodienes 3 also react with enamines 13, 14, and 18 affording pyridine derivatives 16, 17, and 20 in a regioselective fashion. Norbornadiene 11, a less strained olefin than cycloalkenes 7 and 8, requires the presence of lithium perchlorate as catalyst in a nonaqueous solvent like ether, to give cycloadducts 12.
• Preparation and reactivity of electron-poor 2-azadienes. Diels-Alder reaction with trans-cyclooctene.
  作者：Francisco Palacios、Itziar Perez de Heredia、Gloria Rubiales

  DOI：10.1016/s0040-4039(00)79357-9

  日期：1993.7

  Di-, tri- and tetra- substituted 2-azadienes 3 underbar with electron withdrawing groups have been obtained by Aza-Wittig reaction of N-vinylic phosphazenes with carbonyl compounds. The Diels-Alder reaction of 3 underbar with trans-cyclooctene has also been explored.
• Reaction of <i>N</i>-Vinylic Phosphazenes Derived from β-Amino Acids with Aldehydes. Azadiene-Mediated Synthesis of Dihydropyridines, Pyridines, and Polycyclic Nitrogen Derivatives
  作者：Francisco Palacios、Esther Herrán、Gloria Rubiales

  DOI：10.1021/jo9902650

  日期：1999.8.1

  Enamino phosphonium salts 2 are obtained by 1,2-addition of hydrogen chloride to N-vinylic phosphazenes 1 derived from triphenylphosphine. Aza-Wittig reaction of phosphazenes 1 derived from triphenylphosphine and 6 derived from diphenylmethylphosphine with aldehydes 3 leads to the formation of 2-azadienes 7. Reaction of azadienes 7 with enamines affords dihydropyridines 9 and 11, pyridines 12, and bicyclic nitrogen heterocycles 15-18 in a regioselective fashion, while heterodiene 20 reacts in the same way with pyrrolidinocyclohexanone giving 1-azaphenanthrene compound 21. Reaction of enamino phosphonium salts 2 with aldehydes 3 gives symmetrical dihydropyridines 5.