Mechanistic studies on intramolecular C–H trifluoromethoxylation of (hetero)arenes via OCF 3 -migration

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 OCF 3 -containing building blocks. Herein we describe our investi...

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Published in:Organic & biomolecular chemistry 2016, Vol.14 (24), p.5599-5605
Main Authors: Lee, Katarzyna N., Lei, Zhen, Morales-Rivera, Cristian A., Liu, Peng, Ngai, Ming-Yu
Format: Article
Language:English
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Summary: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 OCF 3 -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 OCF 3 -migration step proceeds via a heterolytic cleavage of the N–OCF 3 bond followed by rapid recombination of a short-lived ion pair. Computational studies further support the proposed ion pair reaction pathway for the OCF 3 -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.
ISSN:1477-0520
1477-0539
DOI:10.1039/C6OB00132G