2-(chloromethyl)-1-tosylpyrrolidine | 1275117-03-7

• 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: 2-(chloromethyl)-1-tosylpyrrolidine
• 英文别名: 2-(Chloromethyl)-1-(4-methylphenyl)sulfonylpyrrolidine
• CAS: 1275117-03-7
• 化学式: C₁₂H₁₆ClNO₂S
• 分子量: 273.784
• InChiKey: LZNRFGFXSLSDKU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  45.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(chloromethyl)-1-tosylpyrrolidine 在 sodium azide 、 sodium iodide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以89 %的产率得到2-(Azidomethyl)-1-(4-methylphenyl)sulfonylpyrrolidine
  参考文献：
  名称：

  Catalyst‐free Chloroamination Cyclization Cascade with Sodium Hypochlorite: from N‑(Pentenyl)sulfonylamides to 2‑(1‐Chloromethyl)pyrrolidines

  摘要：

  A mild and catalyst‐free protocol to obtain several 2‐chloromethylpyrrolidines by the use of a commercial solution of sodium hypochlorite is here reported, without the need for a light source. The choice of the solvent revealed to be crucial in the success of the reaction. Mechanistic studies, both experimental and computational, confirmed a radical mechanism, where the deprotonation step, followed by the oxidation of a N‐centered anion to the corresponding radical, allowed 2‐chloromethylpyrrolidines, by a very fast cyclization, to be obtained. Sodium hypochlorite plays the role of both the oxidant and the chlorine source.

  DOI：

  10.1002/ejoc.202400108
• 作为产物：
  描述：

  在 羰基镁 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以34.3 mg的产率得到2-(chloromethyl)-1-tosylpyrrolidine
  参考文献：
  名称：

  酰胺基自由基的产生和反应性：锰介导的原子转移反应。

  摘要：

  已经开发了一种简单有效的方案，可通过锰介导的原子转移反应从胺官能团生成酰胺基。该方法采用了一种富含地球和廉价的锰络合物Mn2（CO）10作为催化剂，并使用了可见光作为能量输入。使用这种策略，脂肪族胺的未活化C（sp3）-H键和未活化烯烃的分子内/分子间氯胺的定点氯化很容易在温和的反应条件下实现，因此可以有效地获得一系列有价值的，氯化的烷基氯化物。吡咯烷和邻氯胺衍生物。这些实际反应显示出广泛的底物范围，并能耐受各种官能团以及包括各种市售药物衍生物在内的复杂分子。

  DOI：

  10.1002/anie.201913042

文献信息

• Regioselective (Diacetoxyiodo)benzene-Promoted Halocyclization of Unfunctionalized Olefins
  作者：Gong-Qing Liu、Yue-Ming Li

  DOI：10.1021/jo501739j

  日期：2014.11.7

  A metal-free method for intramolecular halocyclization of unfunctionalized olefins was detailed. (Diacetoxyiodo)benzene (PIDA) was very effective for haloamidation, haloetherification, and halolactonization of unfunctionalized olefins. In the presence of 1.1 equiv of PIDA and suitable halogen sources, a variety of unfunctionalized olefins could be converted to the corresponding 1,2-bifunctional cyclic

  详细介绍了一种用于非官能化烯烃分子内卤代化的无金属方法。（二乙酰氧基碘）苯（PIDA）对于未官能化烯烃的卤代酰胺化，卤代醚化和卤代内酯化非常有效。在存在1.1当量的PIDA和合适的卤素源的情况下，可以将各种未官能化的烯烃以良好或优异的分离产率转化为相应的1,2-双官能环状骨架，并且可以高收率获得生物学上有意义的化合物的关键中间体通过亲核取代由此获得的卤代环化产物在温和条件下获得收率。
• Highly Selective Palladium-Catalyzed Intramolecular Chloroamination of Unactivated Alkenes by Using Hydrogen Peroxide as an Oxidant
  作者：Guoyin Yin、Tao Wu、Guosheng Liu

  DOI：10.1002/chem.201102776

  日期：2012.1.9

  Cheap and clean! A novel Pd‐catalyzed oxidative intramolecular chloroamination of unactivated alkenes has been developed by using hydrogen peroxide as an oxidant and CaCl2 as a chlorine source. A series of chlorinated piperidine derivatives has been obtained with high regio‐ and diastereoselectivities at room temperature (see scheme).

  便宜又干净！通过使用过氧化氢作为氧化剂和CaCl 2作为氯源，开发了一种新型的Pd催化的未活化烯烃的氧化分子内氯胺化反应。已获得一系列在室温下具有高区域选择性和非对映选择性的氯化哌啶衍生物（参见方案）。
• Brønsted acid-assisted N-alkylation of sulfonamides using ethers as the alkylation reagents
  作者：Wei Shi、Chun-Mei Bai、Kai Zhu、Dong-Mei Cui、Chen Zhang

  DOI：10.1016/j.tet.2013.11.036

  日期：2014.1

  N-Alkylation of sulfonamides using cyclic ethers as alkylation reagents and Bronsted acid as a catalyst produced pyrrolidine and piperidine derivatives in good yields. When using symmetrical and unsymmetrical ethers as alkylation reagents, mono-N-allcylation of sulfonamides took place to afford the corresponding products. (C) 2013 Elsevier Ltd. All rights reserved.
• Generation and Reactivity of Amidyl Radicals: Manganese‐Mediated Atom‐Transfer Reaction
  作者：Run‐Zhou Liu、Jinxia Li、Jun Sun、Xian‐Guan Liu、Shuanglin Qu、Ping Li、Bo Zhang

  DOI：10.1002/anie.201913042

  日期：2020.3.9

  been developed. This approach employs an earth-abundant and inexpensive manganese complex, Mn2 (CO)10 , as the catalyst and visible light as the energy input. Using this strategy, site-selective chlorination of unactivated C(sp3 )-H bonds of aliphatic amines and intramolecular/intermolecular chloroaminations of unactivated alkenes were readily realized under mild reaction conditions, thus providing efficient

  已经开发了一种简单有效的方案，可通过锰介导的原子转移反应从胺官能团生成酰胺基。该方法采用了一种富含地球和廉价的锰络合物Mn2（CO）10作为催化剂，并使用了可见光作为能量输入。使用这种策略，脂肪族胺的未活化C（sp3）-H键和未活化烯烃的分子内/分子间氯胺的定点氯化很容易在温和的反应条件下实现，因此可以有效地获得一系列有价值的，氯化的烷基氯化物。吡咯烷和邻氯胺衍生物。这些实际反应显示出广泛的底物范围，并能耐受各种官能团以及包括各种市售药物衍生物在内的复杂分子。
• Catalyst‐free Chloroamination Cyclization Cascade with Sodium Hypochlorite: from N‑(Pentenyl)sulfonylamides to 2‑(1‐Chloromethyl)pyrrolidines
  作者：Jacopo Scarfiello、Marco Rusconi、Alberto Lanfranco、Emanuele Azzi、Stefano Caracciolo、Giovanni Ghigo、Polyssena Renzi、Annamaria Deagostino

  DOI：10.1002/ejoc.202400108

  日期：——

  A mild and catalyst‐free protocol to obtain several 2‐chloromethylpyrrolidines by the use of a commercial solution of sodium hypochlorite is here reported, without the need for a light source. The choice of the solvent revealed to be crucial in the success of the reaction. Mechanistic studies, both experimental and computational, confirmed a radical mechanism, where the deprotonation step, followed by the oxidation of a N‐centered anion to the corresponding radical, allowed 2‐chloromethylpyrrolidines, by a very fast cyclization, to be obtained. Sodium hypochlorite plays the role of both the oxidant and the chlorine source.