Enhanced Mechanistic Understanding Through the Detection of Radical Intermediates in Organic Reactions
Two applications of a radical trap based on a homolytic substitution reaction (SH2') are presented for the trapping of short-lived radical intermediates in organic reactions. The first example is a photochemical cyanomethylation catalyzed by a Ru complex. Two intermediate radicals in the radica...
| Main Authors: | , , , , , , |
|---|---|
| Format: | Article |
| Language: | deu |
| Published: |
Swiss Chemical Society
2024-03-01
|
| Series: | CHIMIA |
| Subjects: | |
| Online Access: | https://www.chimia.ch/chimia/article/view/7145 |
| _version_ | 1797242890180624384 |
|---|---|
| author | Ivan Ocaña Peter J. H. Williams James Donald Neil Griffin George Hodges Andrew R. Rickard Victor Chechik |
| author_facet | Ivan Ocaña Peter J. H. Williams James Donald Neil Griffin George Hodges Andrew R. Rickard Victor Chechik |
| author_sort | Ivan Ocaña |
| collection | DOAJ |
| description | Two applications of a radical trap based on a homolytic substitution reaction (SH2') are presented for the trapping of short-lived radical intermediates in organic reactions. The first example is a photochemical cyanomethylation catalyzed by a Ru complex. Two intermediate radicals in the radical chain propagation have been trapped and detected using mass spectrometry (MS), along with the starting materials, products and catalyst degradation fragments. Although qualitative, these results helped to elucidate the reaction mechanism. In the second example, the trapping method was applied to study the radical initiation catalyzed by a triethylboronoxygen mixture. In this case, the concentration of trapped radicals was sufficiently high to enable their detection by nuclear magnetic resonance (NMR). Quantitative measurements made it possible to characterize the radical flux in the system under different reaction conditions (including variations of solvent, temperature and concentration) where modelling was complicated by chain reactions and heterogeneous mass transfer.
|
| first_indexed | 2024-04-24T18:46:24Z |
| format | Article |
| id | doaj.art-828a9ceccafc48f2bb1708dc28a35cb3 |
| institution | Directory Open Access Journal |
| issn | 0009-4293 2673-2424 |
| language | deu |
| last_indexed | 2024-04-24T18:46:24Z |
| publishDate | 2024-03-01 |
| publisher | Swiss Chemical Society |
| record_format | Article |
| series | CHIMIA |
| spelling | doaj.art-828a9ceccafc48f2bb1708dc28a35cb32024-03-27T05:18:18ZdeuSwiss Chemical SocietyCHIMIA0009-42932673-24242024-03-0178310.2533/chimia.2024.123Enhanced Mechanistic Understanding Through the Detection of Radical Intermediates in Organic ReactionsIvan Ocaña0Peter J. H. Williams1James Donald2Neil Griffin3George Hodges4Andrew R. Rickard5Victor Chechik6Department of Chemistry, University of York, Heslington, York YO10 5DD, UKDepartment of Chemistry, University of York, Heslington, York YO10 5DD, UKDepartment of Chemistry, University of York, Heslington, York YO10 5DD, UKJealott’s Hill International Research Centre, Syngenta, Bracknell, Berkshire RG42 6EY, UKbJealott’s Hill International Research Centre, Syngenta, Bracknell, Berkshire RG42 6EY, UKDepartment of Chemistry, University of York, Heslington, York YO10 5DD, UK; National Centre for Atmospheric Science, Wolfson Atmospheric Chemistry Laboratories, University of York, Heslington, York, YO10 5DD, UKDepartment of Chemistry, University of York, Heslington, York YO10 5DD, UKTwo applications of a radical trap based on a homolytic substitution reaction (SH2') are presented for the trapping of short-lived radical intermediates in organic reactions. The first example is a photochemical cyanomethylation catalyzed by a Ru complex. Two intermediate radicals in the radical chain propagation have been trapped and detected using mass spectrometry (MS), along with the starting materials, products and catalyst degradation fragments. Although qualitative, these results helped to elucidate the reaction mechanism. In the second example, the trapping method was applied to study the radical initiation catalyzed by a triethylboronoxygen mixture. In this case, the concentration of trapped radicals was sufficiently high to enable their detection by nuclear magnetic resonance (NMR). Quantitative measurements made it possible to characterize the radical flux in the system under different reaction conditions (including variations of solvent, temperature and concentration) where modelling was complicated by chain reactions and heterogeneous mass transfer. https://www.chimia.ch/chimia/article/view/7145Mass spectrometryMechanistic studiesRadical reactionsRadical trapping |
| spellingShingle | Ivan Ocaña Peter J. H. Williams James Donald Neil Griffin George Hodges Andrew R. Rickard Victor Chechik Enhanced Mechanistic Understanding Through the Detection of Radical Intermediates in Organic Reactions CHIMIA Mass spectrometry Mechanistic studies Radical reactions Radical trapping |
| title | Enhanced Mechanistic Understanding Through the Detection of Radical Intermediates in Organic Reactions |
| title_full | Enhanced Mechanistic Understanding Through the Detection of Radical Intermediates in Organic Reactions |
| title_fullStr | Enhanced Mechanistic Understanding Through the Detection of Radical Intermediates in Organic Reactions |
| title_full_unstemmed | Enhanced Mechanistic Understanding Through the Detection of Radical Intermediates in Organic Reactions |
| title_short | Enhanced Mechanistic Understanding Through the Detection of Radical Intermediates in Organic Reactions |
| title_sort | enhanced mechanistic understanding through the detection of radical intermediates in organic reactions |
| topic | Mass spectrometry Mechanistic studies Radical reactions Radical trapping |
| url | https://www.chimia.ch/chimia/article/view/7145 |
| work_keys_str_mv | AT ivanocana enhancedmechanisticunderstandingthroughthedetectionofradicalintermediatesinorganicreactions AT peterjhwilliams enhancedmechanisticunderstandingthroughthedetectionofradicalintermediatesinorganicreactions AT jamesdonald enhancedmechanisticunderstandingthroughthedetectionofradicalintermediatesinorganicreactions AT neilgriffin enhancedmechanisticunderstandingthroughthedetectionofradicalintermediatesinorganicreactions AT georgehodges enhancedmechanisticunderstandingthroughthedetectionofradicalintermediatesinorganicreactions AT andrewrrickard enhancedmechanisticunderstandingthroughthedetectionofradicalintermediatesinorganicreactions AT victorchechik enhancedmechanisticunderstandingthroughthedetectionofradicalintermediatesinorganicreactions |