1,3-Benzyl migration in iminium ions: evidence for a fast free-radical chain reaction
The “exocyclic” 1,3-benzyl shift observed in iminium salts derived from 1-benzyl-1,2,3,4-tetrahydroisoquinolines is related to the “endocyclic” Knabe rearrangement. A crossover experiment, isotopic labelling, the study of initiators and inhibitors as well as DFT calculations of gas-phase model struc...
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| Main Authors: | , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
04 November 2011
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| In: |
European journal of organic chemistry
Year: 2011, Issue: 36, Pages: 7355-7365 |
| ISSN: | 1099-0690 |
| DOI: | 10.1002/ejoc.201101183 |
| Online Access: | Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1002/ejoc.201101183 Verlag, lizenzpflichtig, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/ejoc.201101183 
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| Author Notes: | Nancy Blank, Bernd F. Straub, and Till Opatz |
| Summary: | The “exocyclic” 1,3-benzyl shift observed in iminium salts derived from 1-benzyl-1,2,3,4-tetrahydroisoquinolines is related to the “endocyclic” Knabe rearrangement. A crossover experiment, isotopic labelling, the study of initiators and inhibitors as well as DFT calculations of gas-phase model structures provide evidence for a free-radical pathway under kinetic entropy control that is not affected by “slow” radical traps. |
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| Item Description: | Gesehen am 30.03.2022 Dedicated to Professor Paul Margaretha on the occasion of his retirement |
| Physical Description: | Online Resource |
| ISSN: | 1099-0690 |
| DOI: | 10.1002/ejoc.201101183 |