N-Isobutyliden-pyrrolidinium-perchlorat | 57419-61-1

• 分子结构分类: 有机化合物 - 有机氧化合物 - 有机含氧阴离子化合物
• 英文名称: N-Isobutyliden-pyrrolidinium-perchlorat
• 英文别名: Pyrrolidinium, 1-(2-methylpropylidene)-, perchlorate；1-(2-methylpropylidene)pyrrolidin-1-ium;perchlorate
• CAS: 57419-61-1
• 化学式: C₈H₁₆N*ClO₄
• 分子量: 225.672
• InChiKey: PZARLAHKBXMZIA-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -3.24
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  77.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  N-Isobutyliden-pyrrolidinium-perchlorat 、 lithium,methanidylsulfonylmethane 以 四氢呋喃 为溶剂， 反应 0.17h， 生成 1-(1-methylsulfonyl-3-methyl)-2-butylpyrrolidine
  参考文献：
  名称：

  The LiClO4-Mediated Synthesis of β-(Dialkylamino) Sulfoxides and β-(Dialkylamino) Sulfones by Addition of α-Lithiated Salts of Sulfoxides and Sulfones to Aldehydes and (Trimethylsilyl)dialkylamines

  摘要：

  The LiClO4-mediated one-pot reaction of aldehydes with (trimethylsilyl)dialkyl amines and the lithium salt of sulfoxides or sulfones, affords the corresponding beta-(dialkylamino) sulfoxides and beta-(dialkylamino) sulfones in high yields. The aminosulfoxidation reaction of aliphatic or aromatic aldehydes lacks diastereoselectivity, but the diastereomeric sulfoxides can be separated by HPLC or column chromatography for further use.

  DOI：

  10.1002/(sici)1099-0690(200005)2000:9<1735::aid-ejoc1735>3.0.co;2-a
• 作为产物：
  描述：

  1-三甲硅基吡咯烷 、 异丁醛 在 lithium perchlorate 作用下， 以 乙醚 为溶剂， 反应 0.17h， 生成 N-Isobutyliden-pyrrolidinium-perchlorat
  参考文献：
  名称：

  The LiClO4-Mediated Synthesis of β-(Dialkylamino) Sulfoxides and β-(Dialkylamino) Sulfones by Addition of α-Lithiated Salts of Sulfoxides and Sulfones to Aldehydes and (Trimethylsilyl)dialkylamines

  摘要：

  The LiClO4-mediated one-pot reaction of aldehydes with (trimethylsilyl)dialkyl amines and the lithium salt of sulfoxides or sulfones, affords the corresponding beta-(dialkylamino) sulfoxides and beta-(dialkylamino) sulfones in high yields. The aminosulfoxidation reaction of aliphatic or aromatic aldehydes lacks diastereoselectivity, but the diastereomeric sulfoxides can be separated by HPLC or column chromatography for further use.

  DOI：

  10.1002/(sici)1099-0690(200005)2000:9<1735::aid-ejoc1735>3.0.co;2-a

文献信息

• Enantioselective Formal α-Methylation and α-Benzylation of Aldehydes by Means of Photo-organocatalysis
  作者：Giacomo Filippini、Mattia Silvi、Paolo Melchiorre

  DOI：10.1002/anie.201612045

  日期：2017.4.10

  photoexcitation of enamines to trigger the formation of reactive carbon-centered radicals from iodosulfones, while the ground-state chiral enamines provide effective stereochemical control over the radical trapping process. The phenylsulfonyl moiety, acting as a redox auxiliary group, facilitates the generation of radicals. In addition, it can eventually be removed under mild reducing conditions to reveal methyl

  本文详细描述了醛与(苯磺酰基)烷基碘的光化学有机催化对映选择性α-烷基化。该化学依赖于烯胺的直接光激发来触发碘砜形成以碳为中心的反应性自由基，而基态手性烯胺则对自由基捕获过程提供有效的立体化学控制。苯磺酰基部分作为氧化还原辅助基团，促进自由基的产生。此外，它最终可以在温和的还原条件下被去除，以露出甲基和苄基。
• Mechanism of the Stereoselective α-Alkylation of Aldehydes Driven by the Photochemical Activity of Enamines
  作者：Ana Bahamonde、Paolo Melchiorre

  DOI：10.1021/jacs.6b04871

  日期：2016.6.29

  Herein we describe our efforts to elucidate the key mechanistic aspects of the previously reported enantioselective photochemical α-alkylation of aldehydes with electron-poor organic halides. The chemistry exploits the potential of chiral enamines, key organocatalytic intermediates in thermal asymmetric processes, to directly participate in the photoexcitation of substrates either by forming a photoactive

  在此，我们描述了我们为阐明先前报道的醛与缺电子有机卤化物的对映选择性光化学 α-烷基化的关键机制方面所做的努力。该化学利用手性烯胺（热不对称过程中的关键有机催化中间体）的潜力，通过形成光活性电子供体 - 受体复合物或通过在光吸收后直接达到电子激发态来直接参与底物的光激发。这些光化学机制在温和条件下从闭壳前体产生自由基。同时，基态手性烯胺对对映选择性自由基捕获过程提供有效的立体化学控制。我们结合了传统的光物理研究，核磁共振波谱和动力学研究，以更好地了解控制这些对映选择性光化学催化过程的因素。量子产率的测量表明自由基链机制是有效的，而反应谱分析和速率顺序评估表明烯胺捕获以碳为中心的自由基，形成碳-碳键，作为速率决定因素。我们的动力学研究揭示了光触发引发步骤和自由基链传播流形之间存在微妙的相互作用，两者均由手性烯胺介导。量子产率的测量表明自由基链机制是有效的，而反应谱分析和速率顺序评估表明烯胺捕
• Investigation of the Reaction of Allyl(cyclopentadienyl)iron(II) Dicarbonyl with Iminium Salts:  Synthesis of Ammonium Salts of Substituted Five-Membered-Ring Iron Complexes
  作者：Junes Ipaktschi、Azim Ziyaei Halimehjani、Mohammad R. Saidi

  DOI：10.1021/om060783i

  日期：2007.1.1

  Series of quaternary ammonium salts of substituted five-membered-ring iron complexes were prepared by reaction of allyl(cyclopentadienyl)iron(II) dicarbonyl with iminium salts. Also, reactions of allyl(cyclopentadienyl)iron(II) dicarbonyl with in situ prepared iminium salts afford the same products in good to excellent isolated yields.

  通过使烯丙基（环戊二烯基）二羰基铁（II）与亚胺盐反应制备了一系列取代的五元环铁配合物季铵盐。同样，烯丙基（环戊二烯基）铁（II）二羰基化合物与原位制备的亚胺盐的反应以良好的分离产率很好地提供了相同的产物。
• Reaction of Tungsten η¹-Acetylide Complexes [(η⁵-C₅H₅)(NO)(CO)W−C⋮C−R]Li with Iminium Ions
  作者：Junes Ipaktschi、Javad Mohsseni-Ala、Ansgar Dülmer、Christoph Loschen、Gernot Frenking

  DOI：10.1021/om0491185

  日期：2005.2.1

  of η1-vinylidene complex 1 with an enamine. The reaction of 1 with enamines 2a−e leads to vinylcarbene complexes 3a−e in good yield. The first step of this transformation is a Mannich reaction on the β-carbon atom of alkynyltungsten complexes, generating the expected β-amino-alkylated η1-vinylidene complexes 6. This intermediate reacts further to 3a−e by migration of the hydrogen atom adjacent to the

  研究了烷基炔钨配合物[（CO）（NO）（Cp）W-C⋮C-R] Li（R = H，C 6 H 5，C（CH 3）3）与不同取代的亚胺离子的反应。由于在η的β碳原子上的氢原子的相对高酸度1 -vinylidene配合物[（CO）（NO）（CP）W，C ^ CH 2）]（1），父η 1 -acetylide复杂[（CO）（NO）（CP）-W-C⋮C-H）] -原位同时通过的η反应的亚胺离子生成1 -vinylidene复杂1与烯胺。1与烯胺2a的反应- Ë导致vinylcarbene配合3A - ê以良好的收率。这种转换的第一步是对alkynyltungsten复合物的β碳原子上的曼尼希反应，生成所述预期β氨基烷基化的η 1个-vinylidene络合物6。该中间体进一步反应，以图3a - ë由邻近的氮原子的η的α碳原子上的氢原子的迁移1 -vinylidene部分。一个η的外观1 -viny
• Cleavage of 2-(1,2,3,4-tetrahydroisoquinolin-1-yl)-2-phenyl-1,3-dithianes with HgO/BF3
  作者：E. Gr�n、W. Wiegrebe

  DOI：10.1007/bf00806969

  日期：1997.10

  The title compounds (5) were prepared by addition of 2-phenyl-1,3-dithiane anion (2-lithiated 10) to adequately substituted N-alkyl-3,4-dihydroisoquinolinium salts (7a-7g). Cleavage of compounds 5 with HgO/BF3 affords S-benzoyl-1,3-propanedithiol (4a) and the corresponding disulfide 4c, benzaldehyde, and Hg(I) ions. In contrast to the title compounds, 2-(alpha-dialkylaminobenzyl)-2-phenyl-1 ,3-dithianes (6) yield benzil under these conditions.