Developing an Ionic Halide Transfer and Addition Process Driven by Theoretical and Experimental Synergy.

Authors

Marzieh Bahmani, Kimia Rahmannia, Christopher Richardson, Christopher J T Hyland, Richmond Lee

Published in

The Journal of organic chemistry. Sep 20, 2025. Epub Sep 20, 2025.

Abstract

By combining theoretical and experimental approaches, a novel ionic alternative to the atom transfer radical addition (ATRA) reaction has been developed. Based on the halogenophilic nucleophilic substitution (S_N2X) process, this new base-mediated protocol termed halide transfer and addition (HTA) enables the concurrent formation of C(sp³)-C(sp³) and C(sp³)-X bonds from α-halo carbonyls and electron-deficient alkenes. DFT modeling elucidated the importance of 1,4-dioxane in dissociating the KO^tBu tetramer for reaction initiation and coordination. The K⁺ cation is stabilized by the solvent and can direct reaction progression, leaving the ^tBuO^- anion free to drive the S_N2X, supporting a detailed mechanistic proposal for the HTA process. Experimental studies were conducted to verify theoretical predictions, scope the reactivity, and iteratively improve both the model and mechanistic insight, resulting in a synergistic optimization loop for synthetic chemistry reaction method development.

PMID:
40974339
Bibliographic data and abstract were imported from PubMed on 20 Sep 2025.

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