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Computational Study of Key Mechanistic Details for a Proposed Copper (I)-Mediated Deconstructive Fluorination of N-Protected Cyclic Amines
- Source :
- Topics in catalysis, vol 65, iss 1-4
- Publication Year :
- 2022
- Publisher :
- eScholarship, University of California, 2022.
-
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.
- Subjects :
- Deconstructive fluorination
N-Benzoylated cyclic amines
DFT calculation
Copper catalyst
010402 general chemistry
01 natural sciences
Aldehyde
Medicinal chemistry
Physical Chemistry
Catalysis
chemistry.chemical_compound
Electron transfer
Selectfluor
chemistry.chemical_classification
010405 organic chemistry
Decarbonylation
Iminium
General Chemistry
Chemical Engineering
Oxidative addition
0104 chemical sciences
Dication
chemistry
Two-state reactivity
Hemiaminal
Selectfluor®
Physical Chemistry (incl. Structural)
Subjects
Details
- Database :
- OpenAIRE
- Journal :
- Topics in catalysis, vol 65, iss 1-4
- Accession number :
- edsair.doi.dedup.....7b0f993d802127de9c22932b0e491c1c