Journal Article10.1021/JA017401E
Direct observation of aldehyde insertion into rhodium-aryl and -alkoxide complexes.
Christopher Krug,John F. Hartwig +1 more
111
TL;DR: Reactions of arylrhodium complexes with an excess of aldehyde formed esters by a double insertion and beta-hydrogen elimination sequence andKinetic isotope effects and the formation of diarylmethanols in THF/water mixtures are inconsistent with oxidative addition of the acyl carbon-Hydrogen bond and reductive elimination to form ketone.
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Abstract: Several organorhodium(I) complexes of the general formula (PPh3)2(CO)RhR (R = p-tolyl, o-tolyl, Me) were isolated and were shown to insert aryl aldehydes into the aryl−rhodium(I) bond. Under nonaqueous conditions, these reactions provided ketones in good yield. The stability of the arylrhodium(I) complexes allowed these reactions to be run also in mixtures of THF and water. In this solvent system, diarylmethanols were generated exclusively. Mechanistic studies support the formation of ketone and diarylmethanol by insertion of aldehyde into the rhodium−aryl bond and subsequent β-hydride elimination or hydrolysis to form diaryl ketone or diarylmethanol products. Kinetic isotope effects and the formation of diarylmethanols in THF/water mixtures are inconsistent with oxidative addition of the acyl carbon−hydrogen bond and reductive elimination to form ketone. Moreover, the intermediate rhodium diarylmethoxide formed from insertion of aldehyde was observed directly during the reaction. Its structure was confir...
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Citations
Rhodium-Catalyzed Asymmetric Arylation
TL;DR: The research on these distinct families of chiral ligands are highlighted and their applications in the RCAA of arylmetals to activated alkenes, aldehydes, ketones and imines, and RCAA-tandem reactions are described.
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Rhodium/Copper‐Catalyzed Annulation of Benzimides with Internal Alkynes: Indenone Synthesis through Sequential C ? H and C ? N Cleavage
TL;DR: This novel reaction provides a facile route to synthesize indenones from readily available benzimides and internal alkynes.
301
References
N-methoxy-n-methylamides as effective acylating agents
Steven Nahm,Steven M. Weinreb +1 more
TL;DR: Readily preparable N-methoxy-N-methylamides couple in good yields with Grignard and organolithium reagents to produce ketones, and are reduced with hydrides to afford aldehydes.
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Mechanistic and Synthetic Studies of the Addition of Alkyl Aldehydes to Vinylsilanes Catalyzed by Co(I) Complexes
TL;DR: The mechanistic details of the cobalt-catalyzed intermolecular hydroacylation reaction have been investigated using kinetic, spectroscopic, and crystallographic methods.
170