Catalytic Carbonyl Z-Dienylation via Multicomponent Reductive Coupling of Acetylene to Aldehydes and α-Ketoesters Mediated by Hydrogen: Carbonyl Insertion into Cationic Rhodacyclopentadienes
- 22 November 2006
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 128 (50) , 16040-16041
- https://doi.org/10.1021/ja0664786
Abstract
Exposure of aldehydes or α-ketoesters to equal volumes of acetylene and hydrogen gas at ambient temperature and pressure in the presence of cationic rhodium catalysts provides products of carbonyl Z-butadienylation, which arise via multicomponent coupling of four molecules: two molecules of acetylene, a molecule of vicinal dicarbonyl compound, and a molecule of elemental hydrogen. The collective data suggest a catalytic mechanism involving carbonyl insertion into a cationic rhodacyclopentadiene intermediate derived via oxidative dimerization of acetylene. Hydrogenolytic cleavage of the resulting oxarhodacycloheptadiene via formal σ-bond metathesis provides the product of carbonyl addition and cationic rhodium(I) to close the catalytic cycle. Studies involving the hydrogenation of 1,6-diyne 14a in the presence of α-ketoester 6a corroborate the proposed catalytic mechanism. These multicomponent couplings represent the first use of acetylene gas, a basic chemical feedstock, in metal-catalyzed reductive C−C bond formation.Keywords
This publication has 11 references indexed in Scilit:
- Enantioselective Reductive Cyclization of 1,6-Enynes via Rhodium-Catalyzed Asymmetric Hydrogenation: C−C Bond Formation Precedes Hydrogen ActivationJournal of the American Chemical Society, 2005
- Rhodium-Catalyzed Reductive Cyclization of 1,6-Diynes and 1,6-Enynes Mediated by Hydrogen: Catalytic C−C Bond Formation via Capture of Hydrogenation IntermediatesJournal of the American Chemical Society, 2004
- Direct Observation of Aldehyde Insertion into Rhodium−Aryl and −Alkoxide ComplexesJournal of the American Chemical Society, 2002
- σ Metathesis as a Critical Step for the Transition Metal Catalyzed Formation of Formic Acid from CO2 and H2? An Ab Initio InvestigationAngewandte Chemie International Edition in English, 1995
- Organoyttrium-catalyzed cyclization of substituted 1,5- and 1,6-dienesJournal of the American Chemical Society, 1992
- Catalytic asymmetric synthesis of Secondary (E)‐allyl alcohols from acetylenes and aldehydes via (1‐alkenyl)zinc intermediates. Preliminary CommunicationHelvetica Chimica Acta, 1992
- An .eta.4-benzene species mediates acetylene cyclotrimerizationJournal of the American Chemical Society, 1991
- Diin‐Reaktion, XXXIX1) Synthese von 1,3‐Dihydroisobenzofuranen und 4,6‐Diphenyl‐1H,3H‐thieno[3,4‐c]furan, ‐1H,3H‐selenolo[3,4‐c]furan und ‐1H,3H‐telluro[3,4‐c]furanEuropean Journal of Organic Chemistry, 1976
- Diin‐Reaktion, XIV. Mono‐ und bis‐heterokondensierte Benzochinone: Benz‐, Furo‐, Thieno‐, Selenopheno‐isoindolchinoneEuropean Journal of Inorganic Chemistry, 1972
- Bis-acetylen-Verbindungen, VIII Struktur und reaktives Verhalten von RhodiumkomplexenEuropean Journal of Organic Chemistry, 1972