Formate-Mediated Reductive Cross-Coupling of Vinyl Halides and Aryl Iodides: <i>cine</i>-Substitution via Palladium(I) Catalysis
Formate-mediated reductive cross-couplings of vinyl halides with aryl iodides via palladium(I) catalysis occur with highly uncommon <i>cine</i>-substitution. The active dianionic palladium(I) catalyst, [Pd<sub>2</sub>I<sub>4</sub>][NBu<sub>4</sub>]<sub>2</sub>, is generated <i>in situ</i> from Pd(OAc)<sub>2</sub>, Bu<sub>4</sub>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)<sub>2</sub>(NBu<sub>4</sub>)], which, upon vinyl halide carbopalladation, forms products of <i>cine</i>-substitution by way of palladium(IV) carbenes, as corroborated by deuterium-labeling experiments.
Authors
- Catherine G. Santana (ORCID: https://orcid.org/0000-0001-8135-0149)
- Madeline M. Evarts
- Michael J. Krische (ORCID: https://orcid.org/0000-0001-8418-9709)
- Jonathan Z. Shezaf (ORCID: https://orcid.org/0000-0003-4865-5973)
- Yhin Sarah Teoh (ORCID: https://orcid.org/0009-0004-6687-2466)
Institutions
- The University of Texas at Austin (US)
Publication Details
- Journal
- Organic Letters
- Published
- 2024-08-12
- DOI
- https://doi.org/10.1021/acs.orglett.4c02642
- Citations
- 4
- Primary Topic
- Catalytic Cross-Coupling Reactions
- Type
- article
- Field-Weighted Citation Impact
- 1.00
Funders
- Welch Foundation
- National Institutes of Health
- National Institute of General Medical Sciences