title: Mechanistic studies on intramolecular C-H trifluoromethoxylation of (hetero)arenes via OCF3-migration.
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.
authors.affiliation: Department of Chemistry, Stony Brook University, Stony Brook, New York 11794-3400, USA. ming-yu.ngai@stonybrook.edu and Institute of Chemical Biology and Drug Discovery, Stony Brook University, Stony Brook, New York 11794-3400, USA.
authors.forename: Katarzyna N
authors.initials: KN
authors.lastname: Lee
authors.affiliation: Department of Chemistry, Stony Brook University, Stony Brook, New York 11794-3400, USA. ming-yu.ngai@stonybrook.edu and Institute of Chemical Biology and Drug Discovery, Stony Brook University, Stony Brook, New York 11794-3400, USA.
authors.forename: Zhen
authors.initials: Z
authors.lastname: Lei
authors.affiliation: Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, USA.
authors.forename: Cristian A
authors.initials: CA
authors.lastname: Morales-Rivera
authors.affiliation: Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, USA.
authors.forename: Peng
authors.initials: P
authors.lastname: Liu
authors.affiliation: Department of Chemistry, Stony Brook University, Stony Brook, New York 11794-3400, USA. ming-yu.ngai@stonybrook.edu and Institute of Chemical Biology and Drug Discovery, Stony Brook University, Stony Brook, New York 11794-3400, USA.
authors.forename: Ming-Yu
authors.initials: MY
authors.lastname: Ngai
mesh_terms: D006571:Heterocyclic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D006845:Hydrocarbons, Fluorinated / Q000737:chemistry*; D019811:Hydroxylamine / Q000737:chemistry*; D015394:Molecular Structure; D011789:Quantum Theory
chemical_list: D006571:Heterocyclic Compounds; D006845:Hydrocarbons, Fluorinated; D019811:Hydroxylamine