3-methyl-4-vinyl-1-(4-methylbenzenesulfonyl)pyrrolidine | 835650-93-6

• 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: 3-methyl-4-vinyl-1-(4-methylbenzenesulfonyl)pyrrolidine
• 英文别名: 3-Ethenyl-4-methyl-1-(4-methylbenzene-1-sulfonyl)pyrrolidine；3-ethenyl-4-methyl-1-(4-methylphenyl)sulfonylpyrrolidine
• CAS: 835650-93-6
• 化学式: C₁₄H₁₉NO₂S
• 分子量: 265.376
• InChiKey: YICKDARZXRXWIY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  45.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  N-allyl-N-(2-butenyl)-p-toluenesulfonamide 在 C₃₈H₅₀N₂P₂ 、 [Ni(allyl)(cod)][BARF] 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 生成 3-methyl-4-vinyl-1-(4-methylbenzenesulfonyl)pyrrolidine
  参考文献：
  名称：

  1,6-二烯的立体选择性镍催化环异构化

  摘要：

  描述了基于[Ni（烯丙基）（cod）] [BARF]和Wilke的氮杂膦烯基全部-（R）-1的催化剂体系对1，6-二烯的高度立体选择性环异构化。从对称取代的1,6-二烯形成五元环状产物获得了前所未有的高对映体过量，最高可达91％。对于在末端位置取代的不对称1,6-二烯，也实现了较高的化学和区域选择性，从而再次以合理的非常高的收率获得了五元环状产物。环化异构化产物先后进行硼氢化和exo加氢-亚甲基官能团。实现了有希望的非对映选择性，并且这些反应序列可以一锅法高效进行。

  DOI：

  10.1002/adsc.200800104

文献信息

• Medium-Sized Heterocycle Synthesis by the Use of Synergistic Effects of Ni-NHC and γ-Coordination in Cycloisomerization
  作者：Chun-Yu Ho、Lisi He

  DOI：10.1021/jo5008477

  日期：2014.12.19

  an NHC–NiH catalyst and γ-heteroatom chelation were used together as a basis for 1,n-diene termini differentiation and for nγ-exo-trig (head-to-tail) product selectivity. Heterocycles bearing an exocyclic methylene such as oxepines, thiepines, siloxepines, and oxocanes were synthesized from the corresponding 1,n-dienes by a fine-tuning of the NHC properties. The implication of the underlying hypothesis

  本文介绍了一种过渡金属催化中型杂环的不对称环异构化的新方法。一个NHC-NIH催化剂和γ -杂原子螯合的空间和电子效应作为1的基础，一起使用Ñ -二烯末端分化和Ñ γ -外型- TRIG（头-尾）产物选择性。由相应的1，n通过微调NHC的特性获得-Dienes。在竞争实验中进一步证明了潜在假设的含义，在该竞争实验中，优先形成应变的oxepines，而不是其他竞争的oxa /碳环素。在更苛刻的物理条件下和使用合适的NHC配体，在一个罐中将环外亚甲基产物进一步异构化为区域内环烯烃产物。
• Highly Enantioselective Nickel-Catalyzed Intramolecular Hydroalkenylation of N- and O-Tethered 1,6-Dienes To Form Six-Membered Heterocycles
  作者：Ke Li、Mao-Lin Li、Qi Zhang、Shou-Fei Zhu、Qi-Lin Zhou

  DOI：10.1021/jacs.8b04703

  日期：2018.6.20

  A highly enantioselective nickel-catalyzed intramolecular hydroalkenylation of N- or O-tethered 1,6-dienes was developed by using monodentate chiral spiro phosphoramidite ligands. The reaction provides an efficient and straightforward method for preparing very useful six-membered N- and O-heterocycles with high regioselectivity as well as excellent stereoselectivity from easily accessible starting

  通过使用单齿手性螺亚磷酰胺配体开发了高度对映选择性镍催化的 N 或 O 系链 1,6-二烯的分子内加氢烯基化。该反应提供了一种有效且直接的方法，可以在温和的反应条件下从易于获得的起始材料中制备非常有用的六元 N-和 O-杂环，具有高区域选择性和优异的立体选择性。本研究中开发的手性螺镍催化剂是为数不多的用于非共轭二烯高度对映选择性环化的催化剂之一。
• Photochemical and radical initiator-induced reaction of allylic indium compounds
  作者：Tsunehisa Hirashita、Jiro Tanaka、Ayumi Hayashi、Shuki Araki

  DOI：10.1016/j.tetlet.2004.11.056

  日期：2005.1

  Intramolecular cyclization of allylic radicals generated from allylindium compounds both by photolysis or by the reaction of radical initiators was examined. The photolysis of allylic indium compounds, prepared from 8-bromo- or 8-iodooct-1,6-dienes and powdered indium metal, led to the formation of the 5-exo-trig products. Benzoyl peroxide as a radical initiator was also effective for the cyclization. In contrast

  研究了通过光解或自由基引发剂反应从烯丙基化合物生成的烯丙基自由基的分子内环化。由8-溴或8-碘辛基-1,6-二烯和粉状铟金属制得的烯丙基铟化合物的光解导致形成5- exo- trig产品。过氧化苯甲酰作为自由基引发剂对于环化也是有效的。相反，具有氧化性质的自由基引发剂，例如次氯酸叔丁酯，通过碘原子在铟原子上的氧化而诱导碘化，从而产生碘甲基环戊烷。
• Radical reactions initiated by the photochemical cleavage of carbon–indium bonds of organoindium compounds
  作者：Tsunehisa Hirashita、Ayumi Hayashi、Makoto Tsuji、Jiro Tanaka、Shuki Araki

  DOI：10.1016/j.tet.2008.01.013

  日期：2008.3

  Intra- and intermolecular reactions of carbon-centered radicals generated by photolysis of organoindium compounds were examined. The photolysis of vinylindium compounds and indium acetylides provided vinyl and alkynyl radicals, respectively, which were trapped with ethyl iodoacetate giving the corresponding beta,gamma-unsaturated esters. Allylic indium compounds, prepared from 8-bromo- or 8-iodooct-1,6-dienes and powdered indium metal, underwent an intramolecular radical cyclization to afford the 5-exo-trig product. (c) 2008 Elsevier Ltd. All rights reserved.
• Cationic NHC–Pd (NHC=N-heterocyclic carbene) complex-catalyzed cycloisomerization of dienes
  作者：Young-Jin Song、Il Gu Jung、Harim Lee、Young Tak Lee、Young Keun Chung、Hye-Young Jang

  DOI：10.1016/j.tetlet.2007.06.162

  日期：2007.8

  A variety of [(NHC)Pd( eta(3)-allyl)]Cl (NHC = N-heterocyclic carbene) involving different allyl groups and NHC ligands were synthesized and employed for the cycloisomerization of 1,6-dienes to form cyclic compounds selectively. (c) 2007 Elsevier Ltd. All rights reserved.