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Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
Published on: July 30, 2017
Palladium-Catalyzed Meta-Selective Suzuki Coupling of 3,4-Dichloropyridine through N-Oxidation/Deoxygenation
Xin Han1, Shuo Wen2, Shangxun Zhao2
1Key Laboratory of Danjiangkou Reservoir Area's Aquatic Eco-Environment and Health, Shiyan City, College of Chemical and Environmental Engineering, Hanjiang Normal University, Shiyan 442000, Hubei, China.
None:
The site-selective coupling of polyhalogenated heteroarenes remains a persistent and significant hurdle in synthetic chemistry. Compared with the well-established ortho- and para-selective couplings of dichloropyridine, the meta-selective coupling of dichloropyridine has not been developed until now. Herein, we report an electronic modulation strategy for the palladium-catalyzed meta-selective Suzuki coupling of 3,4-dichloropyridine through N-oxidation/deoxygenation. Density functional theory (DFT) calculations reveal that N-oxide modifies both bond dissociation energies (BDEs) and transition-state barriers, providing a clear mechanistic rationale for this reversal in site selectivity from para-selectivity of pyridine to meta-selectivity of its N-oxide. This work establishes N-oxide-directed electronic modulation as a versatile and complementary method for the modular construction of privileged arylpyridines.
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