Work

Formate-Mediated Reductive Cross-Coupling of Vinyl Halides and Aryl Iodides: cine-Substitution via Palladium(I) Catalysis

Year: 2024

Type: article

Abstract: Formate-mediated reductive cross-couplings of vinyl halides with aryl iodides via palladium(I) catalysis occur with highly uncommon cine -substitution. The active dianionic palladium(I) catalyst, [Pd 2 I 4 ][NBu 4 ] 2, is generated in situ from Pd(OAc) 2, Bu 4 NI, and formate. Oxidative addition of aryl iodide followed by dissociation of the dimer provides the monomeric anionic T-shaped arylpalladium(II) species, [Pd(Ar)(I) 2 (NBu 4 )], which, upon vinyl halide carbopalladation, forms products of cine -substitution by way of palladium(IV) carbenes, as corroborated by deuterium-labeling experiments.

Source: Organic Letters

DOI: 10.1021/acs.orglett.4c02642

Authors: Catherine G. Santana, Yhin Sarah Teoh, Madeline M. Evarts, Jonathan Z. Shezaf, Michael J. Krische

Institution: The University of Texas at Austin

Language: English

Topic: Catalytic Cross-Coupling Reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funders: Welch Foundation, National Institutes of Health, National Institute of General Medical Sciences

Awards: G1076564574, G3277079756, G4622911403, Catalytic C-C Bond Forming Hydrogenations