1-(2-phenylprop-1-en-1-yl)pyrrolidine | 50888-81-8

• 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: 1-(2-phenylprop-1-en-1-yl)pyrrolidine
• 英文别名: 1-(2-Phenylprop-1-en-1-yl)pyrrolidine；1-(2-phenylprop-1-enyl)pyrrolidine
• CAS: 50888-81-8
• 化学式: C₁₃H₁₇N
• 分子量: 187.285
• InChiKey: WRANAUPYVAUXQC-UHFFFAOYSA-N

物化性质

• 沸点：
  298.6±10.0 °C(Predicted)
• 密度：
  1.053±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-(2-phenylprop-1-en-1-yl)pyrrolidine 在 dimethyl sulfide borane 、 双氧水 作用下， 生成 2-苯基-1-丙烯
  参考文献：
  名称：

  Unusual directive effects in the hydroboration of .beta.,.beta.-disubstituted enamines. Conversion of .alpha.-substituted aldehydes to the corresponding alkenes and .beta.-amino alcohols

  摘要：

  A comprehensive study of the conversion of beta,beta-disubstituted enamines into the corresponding alkenes and beta-amino alcohols by hydroboration-elimination and hydroboration-oxidation, respectively, has been carried out. The amine moiety of beta,beta-disubstituted enamines was found to exert a decisive influence on the regioselectivity of the hydroboration reaction involving borane methyl sulfide (BMS). Thus, in the hydroboration of morpholino and piperidino enamines, the boron atom is initially placed predominantly in the alpha-position. Conversely, the pyrrolidino enamines direct the boron atom exclusively to the beta-position. Three oxidizing agents, trimethylamine N-oxide, sodium perborate, and 30% hydrogen peroxide-solid sodium hydroxide, were tried in order to optimize the oxidation of the intermediate organoborane derivatives to the corresponding amino alcohols. Our results clearly indicated that 30% hydrogen peroxide-solid sodium hydroxide is best suited for this transformation. The yield of amino alcohol ranged from good to essentially quantitative. Enamines derived from beta-aryl aldehydes, upon hydroboration with BMS followed by methanolysis and oxidation with neutral hydrogen peroxide, gave the corresponding 1,1-disubstituted alkenes. Contrary to the regioselectivity observed in the hydroboration reactions involving BMS, the hydroboration of beta,beta-disubstituted enamines using 9-borabicyclo[3.3.1]nonane (9-BBN) gave the trialkylborane intermediates in which the boron atom was placed exclusively at the beta-position regardless of the amine moiety of the enamine. These trialkylborane derivatives were very stable and did not undergo the usual elimination reaction with either methanol or sodium hydroxide. However, on thermal decomposition, these afforded the corresponding 1,1-disubstituted alkenes in high yields.

  DOI：

  10.1021/jo00019a043
• 作为产物：
  描述：

  2-phenyl-1-(pyrrolidin-1-yl)propan-1-one 在 bis(triphenylphosphine)carbonyliridium(I) chloride 作用下， 以 甲苯 为溶剂， 反应 0.25h， 生成 1-(2-phenylprop-1-en-1-yl)pyrrolidine
  参考文献：
  名称：

  仲酰胺与叔酰胺的交叉偶联：使用叔酰胺作为烷基碳负离子的替代物进行酮合成

  摘要：

  近年来，在酰胺的直接转化领域取得了令人兴奋的进展，尽管如此，两种酰胺之间的缩合仍然很少，并且仅限于均偶联反应。本文中，我们报道了仲酰胺与叔酰胺的交叉偶联，这可在温和条件下提供酮的合成，并具有使用叔酰胺作为烷基碳负离子的替代物的功能。该方法依赖于由叔酰胺通过用Vaska催化剂催化部分还原叔酰胺而产生的烯胺与由仲酰胺通过三氟甲磺酸酐活化而原位形成的腈离子的偶联，以及随后的甲酰化作用。

  DOI：

  10.1002/cjoc.201900215

文献信息

• Enamines as Surrogates of Alkyl Carbanions for the Direct Conversion of Secondary Amides to α-Branched Ketones
  作者：Yong-Peng Liu、Shu-Ren Wang、Ting-Ting Chen、Cun-Cun Yu、Ai-E Wang、Pei-Qiang Huang

  DOI：10.1002/adsc.201801443

  日期：2019.3.5

  A direct transformation of secondary amides into α‐branched ketones with enamines as soft alkylation reagents was developed. In this reaction, enamines serve as surrogates of alkyl carbanions, rather than the conventional enolates equivalents in the Stork's reactions, which allowed for the easy introduction of alkyl groups with electrophilic functional groups. In the presence of 4 Å molecular sieves

  已开发了以烯胺作为软烷基化试剂将仲酰胺直接转化为α-支链酮的方法。在该反应中，烯胺充当烷基碳负离子的替代物，而不是Stork反应中的常规烯醇式等同物，从而可以轻松引入具有亲电官能团的烷基。在存在4Å分子筛的情况下，该方法可以扩展到仲酰胺与醛的单锅偶联以生成酮。
• Stereochemical Studies. XXIV. Asymmetric Synthesis of optically Active (+)-4-Methyl-4-phenyl-2-cyclohexenone with Enamine Alkylation using Proline Derivatives
  作者：GENJI OTANI、SHUNICHI YAMADA

  DOI：10.1248/cpb.21.2112

  日期：——

  Alkylation of enamines prepared from 2-phenylpropanal and L-proline derivatives, with methyl vinyl ketone, was successful and gave, after hydrolysis and cyclization, optically active (+)-4-methyl-4-phenyl-2-cyclohexanone ((+)-IV). The effects of L-proline derivatives, solvents, and reaction temperature on the alkylation were discussed. Under selected conditions the optical yield reached about 50%. Asymmetric induction was clearly thermodynamically controlled.

  由 2-苯基丙醛和 L-脯氨酸衍生物制备的烯胺与甲基乙烯基酮的烷基化反应获得成功，并在水解和环化后得到了具有光学活性的 (+)-4-methyl-4-phenyl-2-cyclohexanone ((+)-IV) 。讨论了 L-脯氨酸衍生物、溶剂和反应温度对烷基化反应的影响。在选定的条件下，光学产率达到约 50%。不对称诱导明显受热力学控制。
• Blau, K.; Burgemeister, I.; Grasnick, J., Journal fur praktische Chemie (Leipzig 1954), 1991, vol. 333, # 3, p. 455 - 466
  作者：Blau, K.、Burgemeister, I.、Grasnick, J.、Voerckel, V.

  DOI：——

  日期：——