<2,2-(2)H2>pyrrolidine | 694-23-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: <2,2-(2)H2>pyrrolidine
• 英文别名: 2,2-dideuteropyrrolidine；pyrrolidine-2-d₂；2,2-d2-pyrrolidine；2,2-Dideuteriopyrrolidine
• CAS: 694-23-5
• 化学式: C₄H₉N
• 分子量: 73.1063
• InChiKey: RWRDLPDLKQPQOW-SMZGMGDZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  5
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-氨基-3,5-二溴苯甲醛 、 <2,2-(2)H2>pyrrolidine 以 乙醇 为溶剂， 反应 84.0h， 以77%的产率得到
  参考文献：
  名称：

  Metal-Free α-Amination of Secondary Amines: Computational and Experimental Evidence for Azaquinone Methide and Azomethine Ylide Intermediates

  摘要：

  We have performed a combined computational and experimental study to elucidate the mechanism of a metal-free alpha-amination of secondary amines. Calculations predicted azaquinone methides and azomethine ylides as the reactive intermediates and showed that iminium ions are unlikely to participate in these transformations. These results were confirmed by experimental deuterium-labeling studies and the successful trapping of the postulated azomethine ylide and azaquinone methide intermediates. In addition, computed barrier heights for the rate-limiting step correlate qualitatively with experimental findings.

  DOI：

  10.1021/jo400483h
• 作为产物：
  描述：

  2-吡咯烷酮 在 lithium aluminium deuteride 作用下， 以 乙醚 为溶剂， 反应 16.0h， 生成 <2,2-(2)H2>pyrrolidine
  参考文献：
  名称：

  通过酰胺的亲电活化直接合成烯酰胺

  摘要：

  报道了一种新型的酰胺一步 N-脱氢生成烯酰胺的方法。该反应采用了LiHMDS和三氟甲磺酸酐的不太可能的组合，三氟甲磺酸酐既充当亲电子活化剂又充当氧化剂，其特点是装置简单和底物范围广泛。所形成的烯酰胺的合成效用很容易在一系列下游转化中得到证明。

  DOI：

  10.1021/jacs.1c04363

文献信息

• Intramolecular Redox-Triggered CH Functionalization
  作者：Igor D. Jurberg、Bo Peng、Eckhard Wöstefeld、Maximilian Wasserloos、Nuno Maulide

  DOI：10.1002/anie.201108639

  日期：2012.2.20

  Sacrifice for the team: A one‐pot method achieves remote functionalization at the α‐position of an amine moiety through the sacrificial reduction of a neighboring group. The process takes advantage of an intramolecular redox reaction, thereby avoiding the need for any external oxidants. This method was applied to a concise five‐step total synthesis of indolizidine 167B.

  对团队的牺牲：单锅法通过牺牲性还原相邻基团，在胺部分的α位实现远程官能化。该方法利用了分子内的氧化还原反应，从而避免了任何外部氧化剂的需要。该方法用于简明的吲哚并啶167B的五步全合成。
• Coordination-Induced N–H Bond Weakening in a Molybdenum Pyrrolidine Complex: Isotopic Labeling Provides Insight into the Pathway for H₂ Evolution
  作者：Máté J. Bezdek、István Pelczer、Paul J. Chirik

  DOI：10.1021/acs.organomet.0c00471

  日期：2020.8.24

  pyrrolidine in [(PhTpy)(PPh2Me)2Mo(NH(pyrr))][BArF24] ([1-NH(pyrr)]+; PhTpy = 4′-Ph-2,2′,6′,2″-terpyridine, NH(pyrr) = pyrrolidine, ArF24 = [C6H3-3,5-(CF3)2]4) was determined to be between 41 and 51 kcal mol–1 by thermochemical analysis and supported by a density functional theory (DFT) computed value of 48 kcal mol–1. The complex [1-NH(pyrr)]+ underwent proton-coupled electron transfer (PCET) to 2,4,6-tr

  阳离子钼吡咯烷配合物的合成和表征被描述为显示出显着的配位诱导的NH键弱化。[[ Ph Tpy）（PPh 2 Me）2 Mo（NH（pyrr））] [BArF 24 ]（[1-NH（pyrr）] +中的配位吡咯烷的N–H键解离自由能（BDFE）；Ph Tpy = 4'-Ph-2,2'，6'，2''-吡啶，NH（pyrr）=吡咯烷，ArF 24 = [C 6 H 3 -3,5-（CF 3）2 ] 4）为确定在41至51 kcal mol –1之间通过热化学分析并得到密度泛函理论（DFT）的支持，计算值为48 kcal mol –1。复杂的[1-NH（吡咯）] +后行质子偶联电子转移（PCET）2,4,6-三-叔-butylphenoxyl基团，以及自发ħ 2在温和加热演化以提供相应的钼吡咯烷络合物[（Ph Tpy）（PPh 2 Me）2 Mo（N（pyrr））] [BArF 24 ]（[1-N（pyrr）]
• Murata, Satoru; Miura, Masahiro; Nomura, Masakatsu, Journal of the Chemical Society. Perkin transactions I, 1987, p. 1259 - 1262
  作者：Murata, Satoru、Miura, Masahiro、Nomura, Masakatsu

  DOI：——

  日期：——
• Direct Synthesis of Enamides via Electrophilic Activation of Amides
  作者：Philipp Spieß、Martin Berger、Daniel Kaiser、Nuno Maulide

  DOI：10.1021/jacs.1c04363

  日期：2021.7.21

  A novel, one-step N-dehydrogenation of amides to enamides is reported. This reaction employs the unlikely combination of LiHMDS and triflic anhydride, which serves as both the electrophilic activator and the oxidant, and is characterized by its simple setup and broad substrate scope. The synthetic utility of the formed enamides was readily demonstrated in a range of downstream transformations.

  报道了一种新型的酰胺一步 N-脱氢生成烯酰胺的方法。该反应采用了LiHMDS和三氟甲磺酸酐的不太可能的组合，三氟甲磺酸酐既充当亲电子活化剂又充当氧化剂，其特点是装置简单和底物范围广泛。所形成的烯酰胺的合成效用很容易在一系列下游转化中得到证明。
• Metal-Free α-Amination of Secondary Amines: Computational and Experimental Evidence for Azaquinone Methide and Azomethine Ylide Intermediates
  作者：Arne Dieckmann、Matthew T. Richers、Alena Yu. Platonova、Chen Zhang、Daniel Seidel、K. N. Houk

  DOI：10.1021/jo400483h

  日期：2013.4.19

  We have performed a combined computational and experimental study to elucidate the mechanism of a metal-free alpha-amination of secondary amines. Calculations predicted azaquinone methides and azomethine ylides as the reactive intermediates and showed that iminium ions are unlikely to participate in these transformations. These results were confirmed by experimental deuterium-labeling studies and the successful trapping of the postulated azomethine ylide and azaquinone methide intermediates. In addition, computed barrier heights for the rate-limiting step correlate qualitatively with experimental findings.