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Updated: Jan 15, 2026

A Microwave-Assisted Direct Heteroarylation of Ketones Using Transition Metal Catalysis
Published on: February 16, 2020
Unconventional β-Hydride Elimination in Pd-Catalyzed Migratory Cyclization: A Theoretical Study of Outer-Sphere
Lin Zhang1, Ya-Nan Wang1, Shihan Liu2
1School of Chemistry and Chemical Engineering, Chongqing Key Laboratory of Chemical Theory and Mechanism, Chongqing University, Chongqing, 401331, P. R. China.
Abstract:
The density functional theory (DFT) study reveals a novel mechanism for Pd-catalyzed C(sp2)-H activation through an unconventional outer-sphere deprotonation pathway. The canonical β-hydride elimination in alkenyl-Pd systems has been unequivocally demonstrated to be both kinetically and thermodynamically unfavorable. Our computational analysis reveals this energetic penalty stems from three key factors: (1) increased ring strain in the four-membered transition state, (2) stronger Pd-C bonding due to π-backdonation in alkenyl-Pd species, and (3) thermodynamic instability of the resulting Pd-H intermediate. This work elucidates a general mechanism for overcoming the longstanding challenge of β-C(sp2)-H activation in alkenyl-metal systems, providing new insights for future development of C-H functionalization reactions.
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