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

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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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Acknowledgements

This work was supported by the National Science Foundation under the CCI Center for Selective C–H Functionalization (CHE-1700982). R.S. is grateful to the NIGMS (R35 GM130345A) for support of the experimental work that was the basis for this computational study. The authors gratefully acknowledge the use of the resources of the Cherry Emerson Center for Scientific Computation at Emory University. J.B.R. thanks Bristol-Myers Squibb for a graduate fellowship.

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  1. Cherry L. Emerson Center for Scientific Computation, Department of Chemistry, Emory University, Atlanta, GA, 30322, USA

    Alexey L. Kaledin & Djamaladdin G. Musaev

  2. Department of Chemistry, University of California, Berkeley, CA, 94720, USA

    Jose B. Roque & Richmond Sarpong

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  1. Alexey L. Kaledin
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Kaledin, A.L., Roque, J.B., Sarpong, R. et al. Computational Study of Key Mechanistic Details for a Proposed Copper (I)-Mediated Deconstructive Fluorination of N-Protected Cyclic Amines. Top Catal 65, 418–432 (2022). https://doi.org/10.1007/s11244-021-01443-y

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