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• W2074493729 endingPage "1091" @default.
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• W2074493729 abstract "[Rh((R)-DTBM-SEGPHOS)]BF4 catalyzes the intramolecular hydroacylation of ketones to afford seven-membered lactones in large enantiomeric excess. Herein, we present a combined experimental and theoretical study to elucidate the mechanism and origin of selectivity in this C−H bond activation process. Evidence is presented for a mechanistic pathway involving three key steps: (1) rhodium(I) oxidative addition into the aldehyde C−H bond, (2) insertion of the ketone C═O double bond into the rhodium hydride, and (3) C−O bond-forming reductive elimination. Kinetic isotope effects and Hammett plot studies support that ketone insertion is the turnover-limiting step. Detailed kinetic experiments were performed using both 1,3-bis(diphenylphosphino)propane (dppp) and (R)-DTBM-SEGPHOS as ligands. With dppp, the keto-aldehyde substrate assists in dissociating a dimeric precatalyst 8 and binds an active monomeric catalyst 9. With [Rh((R)-DTBM-SEGPHOS)]BF4, there is no induction period and both substrate and product inhibition are observed. In addition, competitive decarbonylation produces a catalytically inactive rhodium carbonyl species that accumulates over the course of the reaction. Both mechanisms were modeled with a kinetics simulation program, and the models were consistent with the experimental data. Density functional theory calculations were performed to understand more elusive details of this transformation. These simulations support that the ketone insertion step has the highest energy transition state and reveal an unexpected interaction between the carbonyl-oxygen lone pair and a Rh d-orbital in this transition state structure. Finally, a model based on the calculated transition-state geometry is proposed to rationalize the absolute sense of enantioinduction observed using (R)-DTBM-SEGPHOS as the chiral ligand." @default.
• W2074493729 created "2016-06-24" @default.
• W2074493729 creator A5022187815 @default.
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• W2074493729 creator A5038963306 @default.
• W2074493729 creator A5046679480 @default.
• W2074493729 date "2009-01-07" @default.
• W2074493729 modified "2023-10-18" @default.
• W2074493729 title "Mechanistic Insights into the Rhodium-Catalyzed Intramolecular Ketone Hydroacylation" @default.
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• W2074493729 doi "https://doi.org/10.1021/ja806758m" @default.
• W2074493729 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/19128061" @default.
• W2074493729 hasPublicationYear "2009" @default.
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