2-甲基-1-吡咯烷-1-戊烯 | 147050-25-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 中文名称: 2-甲基-1-吡咯烷-1-戊烯
• 英文名称: 2-Methyl-1-pyrrolidino-1-pentene
• 英文别名: 1-(2-methylpent-1-en-1-yl)pyrrolidine；1-(2-methylpent-1-enyl)pyrrolidine
• CAS: 147050-25-7
• 化学式: C₁₀H₁₉N
• 分子量: 153.268
• InChiKey: DDOWKTKXJFLNET-UHFFFAOYSA-N

物化性质

• 沸点：
  221.9±7.0 °C(Predicted)
• 密度：
  0.928±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 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：

  2-甲基-1-吡咯烷-1-戊烯 在 9-borabicyclo[3.3.1]nonane dimer 作用下， 生成 异己烯
  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

文献信息

• Inverse hydride shuttle catalysis enables the stereoselective one-step synthesis of complex frameworks
  作者：Immo Klose、Giovanni Di Mauro、Dainis Kaldre、Nuno Maulide

  DOI：10.1038/s41557-022-00991-4

  日期：2022.11

  into valuable azabicyclic scaffolds based on the concept of inverse hydride shuttle catalysis. The ternary complexes are readily constructed in situ from three simple precursors and enable a highly modular installation of various substitution patterns. Upon subjection to a unique dual-catalytic system, the transient intermediates undergo an unusual hydride shuttle process that is initiated by a hydride

  从简单的前体一步一步快速组装复杂的支架被认为是效率和可持续性方面的理想反应。事实上，尽管该学科取得了巨大进步，但复杂生物碱框架的直接单步合成仍然是有机化学核心的一个未解决问题。在此，我们提出了一种广泛的策略，其中基于逆氢化物穿梭催化的概念，将动态组装的三元配合物转化为有价值的氮杂双环支架。三元复合物很容易从三个简单的前体原位构建，并能够高度模块化地安装各种替代模式。经受独特的双催化系统，瞬时中间体经历了一个不寻常的氢化物穿梭过程，该过程由氢化物捐赠事件引发。此外，我们表明，结合不对称有机催化，产物生物碱框架获得了优异的光学纯度。