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Keywords:

  • Science & Technology
  • Physical Sciences
  • Chemistry, Applied
  • Chemistry, Physical
  • Chemistry
  • Deconstructive fluorination
  • N-Benzoylated cyclic amines
  • Copper catalyst
  • Selectfluor (R)
  • DFT calculation
  • Two-state reactivity
  • C-H ACTIVATION
  • EFFECTIVE CORE POTENTIALS
  • AB-INITIO
  • STEREOSELECTIVE FUNCTIONALIZATION
  • ELECTROPHILIC FLUORINATION
  • MOLECULAR CALCULATIONS
  • ELECTRONIC-STRUCTURE
  • 2-STATE REACTIVITY
  • BOND-CLEAVAGE
  • ACID LIGANDS

Computational Study of Key Mechanistic Details for a Proposed Copper (I)-Mediated Deconstructive Fluorination of N-Protected Cyclic Amines

Tools:

Journal Title:

TOPICS IN CATALYSIS

Volume:

Volume 65, Number 1-4

Publisher:

, Pages 418-432

Type of Work:

Article

Abstract:

Using calculations, we show that a proposed Cu(I)-mediated deconstructive fluorination of N-benzoylated cyclic amines with Selectfluor® is feasible and may proceed through: (a) substrate coordination to a Cu(I) salt, (b) iminium ion formation followed by conversion to a hemiaminal, and (c) fluorination involving C–C cleavage of the hemiaminal. The iminium ion formation is calculated to proceed via a F-atom coupled electron transfer (FCET) mechanism to form, formally, a product arising from oxidative addition coupled with electron transfer (OA + ET). The subsequent β-C–C cleavage/fluorination of the hemiaminal intermediate may proceed via either ring-opening or deformylative fluorination pathways. The latter pathway is initiated by opening of the hemiaminal to give an aldehyde, followed by formyl H-atom abstraction by a TEDA2+ radical dication, decarbonylation, and fluorination of the C3-radical center by another equivalent of Selectfluor®. In general, the mechanism for the proposed Cu(I)- mediated deconstructive C–H fluorination of N-benzoylated cyclic amines (LH) by Selectfluor® was calculated to proceed analogously to our previously reported Ag(I)-mediated reaction. In comparison to the Ag(I)-mediated process, in the Cu(I)-mediated reaction the iminium ion formation and hemiaminal fluorination have lower associated energy barriers, whereas the product release and catalyst re-generation steps have higher barriers.
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