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Mechanistic studies on intramolecular C-H trifluoromethoxylation of (hetero)arenes via OCF3-migration.
- Source :
-
Organic & biomolecular chemistry [Org Biomol Chem] 2016 Jun 15; Vol. 14 (24), pp. 5599-605. - Publication Year :
- 2016
-
Abstract
- The one-pot two-step intramolecular aryl and heteroaryl C-H trifluoromethoxylation recently reported by our group has provided a general, scalable, and operationally simple approach to access a wide range of unprecedented and valuable OCF3-containing building blocks. Herein we describe our investigations to elucidate its reaction mechanism. Experimental data indicate that the O-trifluoromethylation of N-(hetero)aryl-N-hydroxylamine derivatives is a radical process, whereas the OCF3-migration step proceeds via a heterolytic cleavage of the N-OCF3 bond followed by rapid recombination of a short-lived ion pair. Computational studies further support the proposed ion pair reaction pathway for the OCF3-migration process. We hope that the current study would provide useful insights for the development of new transformations using versatile N-(hetero)aryl-N-hydroxylamine synthons.
Details
- Language :
- English
- ISSN :
- 1477-0539
- Volume :
- 14
- Issue :
- 24
- Database :
- MEDLINE
- Journal :
- Organic & biomolecular chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 27043815
- Full Text :
- https://doi.org/10.1039/c6ob00132g