Work

A ligand-controlled regiodivergent three-component Heck-Tsuji reaction utilizing umpolung hydrazones enabled by palladium catalysis

Year: 2026

Type: article

Abstract: Developing sustainable, selective strategies for the multicomponent functionalization of allenes remains an ongoing challenge in synthetic chemistry. We report a ligand-controlled, regiodivergent palladium-catalyzed three-component Heck-Tsuji reaction of allenes, aryl iodides, and umpolung hydrazones. Leveraging the umpolung reactivity of hydrazones as sustainable carbanion surrogates enables the direct arylalkylation of allenes, forming two C-C bonds in a single step. The ligand environment governs reaction outcomes, switching selectivity between branched and linear adducts using simple, commercially available ligands. This method tolerates a wide range of aryl, heteroaryl, and alkyl substrates, operates under mild conditions, and is amenable to late-stage diversification of complex molecules. Computational studies suggest a plausible explanation for the mechanistic basis of the ligand-dependent regioselectivity, providing reasonable insights for design of divergent Pd-catalyzed multicomponent coupling reactions.

Source: Nature Communications

DOI: 10.1038/s41467-026-76749-0

Authors: Evan F. W. Chen, Ruofei Cheng, Faraz Alaghemand, Rustam Z. Khaliullin, Chao-Jun Li

Institutions: Centre in Green Chemistry and Catalysis, McGill University

Language: English

Topic: Catalytic Cross-Coupling Reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: gold

Estimated APC paid: $6,990