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Bypassing β-Hydride Elimination: Excited-State Pd-Catalyzed C(sp3)–C(sp2) Coupling at Room Temperature

delete2025-11-10
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PRE
AI
K
Kuntal Pal
R
Rajesh Kancherla
S
Sayan Dutta
S
Serik Zhumagazy
B
Bholanath Maity
L
Luigi Cavallo *
M
Magnus Rueping *
DOI：10.1002/anie.202522979delete
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Abstract

Abstract

En 中文
Catalytic modification of C−H bonds using palladium is highly appealing, but transformations involving alkyl-Pd(II) intermediates with β-hydrogens are challenging due to the propensity for β-hydride elimination. To address this, selective arylation of sp3 C−H bonds in amides and alcohols has been achieved using divalent palladium as an excited-state transition metal (TM) species at room temperature. Our approach unveils a non-redox-neutral pathway to achieve C(sp3)–C(sp2) cross-couplings, utilizing aryl iodides as both hydrogen atom transfer (HAT) and arylating agents for the first time under Pd-photochemical conditions. The mechanism involves photo-induced Pd(II)-catalyzed aryl radical generation, HAT, and aryl migration, effectively bypassing the common β-hydride elimination and annulation pathways. Mechanistic investigations using isotope-labeled compounds and density functional theory (DFT) studies support the mechanistic rationale, affirming both the feasibility and intricacies of this effective transformation.
Keywords:
Aryl migration
C(sp3)–C(sp2) cross-coupling
Desulfonylation
DFT calculations
Hydrogen atom transfer (HAT)
Palladium

Journal

Angewandte Chemie-International Edition cover
Angewandte Chemie-International Edition
IF:
16.9
Papers:
5.6W
Citations:
53.0W

Organization

No organization information available