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Rhodium-NHC-Catalyzed gem-Specific O-Selective Hydropyridonation of Terminal Alkynes.

María Galiana-CameoRaúl RomeoAsier UrriolabeitiaVincenzo PassarelliJesús J Pérez-TorrenteVictor PoloRicardo Castarlenas
Published in: Angewandte Chemie (International ed. in English) (2022)
The dinuclear complex [Rh(μ-Cl)(η 2 -coe)(IPr)] 2 is an efficient catalyst for the O-selective Markovnikov-type addition of 2-pyridones to terminal alkynes. DFT calculations support a hydride-free pathway entailing intramolecular oxidative protonation of a π-alkyne by a κ 1 N-hydroxypyridine ligand. Subsequent O-nucleophilic attack on a metallacyclopropene species affords an O-alkenyl-2-oxypyridine chelate rhodium intermediate as the catalyst resting state. The release of the alkenyl ether is calculated as the rate-determining step.
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