September 29, 2021 Journal article Closed Access

Helbing, Tim; Georg, Mats; Stöhr, Fabian; Carraro, Caterina; Becker, Jonathan; Gatto, Barbara; Göttlich, Richard

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{
  "DOI": "10.1002/ejoc.202101072", 
  "abstract": "AbstractThe present study describes the kinetic analysis of the 3\u2010chloropiperidine alkylation mechanism. These nitrogen mustard\u2010based compounds are expected to react via a highly electrophilic bicyclic aziridinium ion, which is readily attacked by nucleophiles. Halide abstraction using silver salts with weakly coordinating anions lead to the isolation of these proposed intermediates, whereas their structure was confirmed by single crystal XRD. Kinetic studies of the aziridinium ions also revealed notable reactivity differences of the C5 gem\u2010methylated compounds and their unmethylated counterparts. The observed reactivity trends were also reflected by NMR studies in aqueous solution and DNA alkylation experiments of the related 3\u2010chloropiperidines. Therefore, the underlying Thorpe\u2010Ingold effect might be considered as another option to adjust the alkylation activity of these compounds.", 
  "author": [
    {
      "family": "Helbing, Tim"
    }, 
    {
      "family": "Georg, Mats"
    }, 
    {
      "family": "St\u00f6hr, Fabian"
    }, 
    {
      "family": "Carraro, Caterina"
    }, 
    {
      "family": "Becker, Jonathan"
    }, 
    {
      "family": "Gatto, Barbara"
    }, 
    {
      "family": "G\u00f6ttlich, Richard"
    }
  ], 
  "id": "207882", 
  "issued": {
    "date-parts": [
      [
        2021, 
        9, 
        29
      ]
    ]
  }, 
  "language": "eng", 
  "title": "Understanding the Alkylation Mechanism of 3\u2010Chloropiperidines \u2013 NMR Kinetic Studies and Isolation of Bicyclic Aziridinium Ions", 
  "type": "article-journal"
}