(R)-N-ethylidene-N-(1-phenylethyl)amine | 37696-13-2

• 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: (R)-N-ethylidene-N-(1-phenylethyl)amine
• 英文别名: N-[(1R)-1-phenylethyl]ethanimine
• CAS: 37696-13-2
• 化学式: C₁₀H₁₃N
• 分子量: 147.22
• InChiKey: HDOBDKNMHQDTSW-SECBINFHSA-N

物化性质

• 沸点：
  222.4±23.0 °C(Predicted)
• 密度：
  0.87±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  12.4
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (R)-N-ethylidene-N-(1-phenylethyl)amine 在 sodium tetrahydroborate 、 potassium carbonate 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 4.0h， 生成 (R)-(+)-N-ethyl-N-propargyl-1-phenyl-ethylamine
  参考文献：
  名称：

  Diastereoselective carbozincation of propargylic amines

  摘要：

  The carbometalation of propargylic amines derived from methylbenzylamine takes place with good 1,3-diastereoselection in the presence of Lewis acids. (C) 2001 Elsevier Science Ltd, All rights reserved.

  DOI：

  10.1016/s0040-4020(01)00069-2
• 作为产物：
  描述：

  R(+)-alpha-甲基苄胺 、 乙醛 生成 (R)-N-ethylidene-N-(1-phenylethyl)amine
  参考文献：
  名称：

  通过α，β-不饱和酰基在胺氮上的自由基取代反应合成内酰胺。

  摘要：

  [反应：见正文]在氮原子上被α，β-不饱和酰基取代，同时消除了α-苯乙基。该反应导致开发了用于五元至七元环内酰胺的新的羰基环化方法。

  DOI：

  10.1021/ol070080c

文献信息

• Asymmetric syntheses of amino acids by addition of cyanide to the schiff bases in the presence of cyanide-modified hemin-copolymer
  作者：Kiyoshi Saito、Kaoru Harada

  DOI：10.1016/s0040-4039(01)80738-3

  日期：1989.1

  Sterically controlled addition reactions of CN group to the Schiff bases by using CN-modified hemin-copolymer were carried out, and the optical yields (80–95 e.e.) of the resulting amino acids were much higher than that obtained without hemin-copolymer.

  使用CN修饰的血红素共聚物进行了CN基团与Schiff碱的立体控制加成反应，所得氨基酸的旋光产率（80-95 ee）比不含血红素共聚物的光学产率高得多。
• Facial diastereoselectivity in the photocycloaddition of chiral N-acyl enamines to benzaldehyde
  作者：Thorsten Bach、Jürgen Schröder、Trixie Brandl、Jürgen Hecht、Klaus Harms

  DOI：10.1016/s0040-4020(98)00161-6

  日期：1998.4

  4-benzyloxazolidinone (15) by vinylation. Their photocycloadditons to benzaldehyde proceeded smoothly and yielded the corresponding oxetanes 12 and 16 (70–80%). A remarkable discrepancy in the course of the reaction was observed. Whereas oxetane formation from 6 proceeded with low diastereoselectivity (30% de) the Paternò-Büchi reaction of compound 7 gave predominantly one diastereoisomer 16a (62% de) the

  在手性的光致面部非对映选择性Ñ酰基烯胺5，6，和7至苯甲醛进行了研究。衍生自α-苯乙胺（8）的烯酰胺5以良好的总收率（74％）得到了相应的氧杂环丁烷，但非对面选择不令人满意（32％de）。所述Ñ -vinyloxazolidinones 6和7从父手性4-苯基- （制备11）或4- benzyloxazolidinone（15）由乙烯化。他们对苯甲醛的光环加成反应进展顺利，并生成相应的氧杂环丁烷12和16（70–80％）。在反应过程中观察到明显的差异。而由6形成的氧杂环丁烷以低的非对映选择性（30％de）进行，化合物7的Paternò-Büchi反应主要产生一种非对映异构体16a（62％de），其相对构型与由恶唑烷二酮6获得的主要非对映异构体12a相反。
• Synthesis of (−)-coniine and (−)-pipecoline using ruthenium catalyzed ring closing metathesis
  作者：Kandasamy Pachamuthu、Yashwant D Vankar

  DOI：10.1016/s0022-328x(00)00930-x

  日期：2001.4

  Ring closing metathesis employing the well-known Grubbs’ ruthenium catalyst has been used as the key step in the synthesis of piperidine alkaloids, (−)-coniine and (−)-pipecoline, and the asymmetric induction has been performed by using (R)-α-methyl benzylamine as an auxiliary.

  采用哌啶类生物碱，（-）-亚氨酸和（-）-胡椒碱合成的关键步骤是采用众所周知的Grubbs钌催化剂进行的闭环复分解，并且已经通过使用（R）进行了不对称诱导。-α-甲基苄胺为助剂。
• ZON, Jerzy, Polish Journal of Chemistry, 1981, vol. 55, # 3, p. 643 - 646
  作者：ZON, Jerzy

  DOI：——

  日期：——
• Enantioselective synthesis of 3-amino-2-azetidinones via the ester enolate - imine condensation
  作者：Fred H. Van der Steen、Henk Kleijn、George J. P. Britovsek、Johann T. B. H. Jastrzebski、Gerard Van Koten

  DOI：10.1021/jo00040a034

  日期：1992.7

  Three approaches to the enantioselective synthesis of 3-amino-4-substituted-2-azetidinones by condensation of alpha-amino ester enolates with imines are described: (i) application of chiral ester derivatives of NN-diethylglycine; (ii) application of chiral N-(alpha-methylbenzyl)imines; and (iii) application of chiral imines derived from (2R)-2,3-O-isopropylideneglyceraldehyde. Zinc and aluminum enolates of (-)-menthyl- and (-)-bornyl NN-diethylglycine esters react with simple imines to selectively afford trans-3-(diethylamino)-2-azetidinones, but with a low chiral induction (ee 0-35%). However, reactions of the metal (Li, Zn, Al) ester enolates of (2,2,5,5-tetramethyl-1-aza-2,4-disilacyclopent-1-yl)acetic acid ethyl ester (1c) with N-(alpha-methylbenzyl)imines yield N-protected 3-amino-2-azetidinones in excellent yields and with very high diastereo- and enantioselectivities. The best results are obtained for the zinc-mediated reactions. For example, trans-(3R,4S)-1(R)-(alpha-methylbenzyl)-3-(2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentyl)-4-[N-(R)-(alpha-methylbenzyl)imino]-2-azeti dineone (4a), a fully protected key intermediate (having the unnatural C-3 configuration) for the synthesis of known monobactam and bicyclic beta-lactam antibiotics, was synthesized in 91% yield with an ee of 91%. Application of chiral imines derived from acetaldehyde and propionaldehyde enable, depending on the solvent, the selective high yielding synthesis (de 60-99%; ee >95%) of any one of the four stereoisomers of 3-amino-4-alkyl-2-azetidinones, which are key intermediates for the synthesis of Aztreonam and related antibiotics. In Et2O, a weakly polar solvent, the trans isomers are formed, whereas the use of a polar THF/HMPA solvent mixture results in formation of the cis isomers. Reaction of the zinc enolate of 1c with the N-(4-methoxyphenyl)imine derivative 2i of (2R)-2,3-O-isopropylidene glyceraldehyde affords trans-(3R,4S)-3-amino-4-[(1'S)-1',2'-O-isopropylideneethyl]-2-azetidinone (10a) in excellent yield (de 86%; ee >98%), whereas reaction of the lithium enolate of 1c with the N-(trimethylsilyl)imine derivative 21 affords the cis-(3S,4S) isomer 10d (key intermediate for the synthesis of Carumonam) in good yield (de >90%; >90%). A rationale for the observed stereoselectivities in terms of highly ordered transition states is presented.