A Rh-catalyzed formal [4 + 1]-cycloaddition approach toward spirooxindole cyclopentenones is described. The diastereoselective cyclopropanation of vinyl ketenes with diazooxindoles as C1 synthons initiated a relatively mild formal [1,3]-migration of an intermediate cyclopropyl ketene to provide spirooxindoles in good to excellent yields (36-99%).
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DFT study on the mechanism of phosphine-catalyzed ring-opening reaction of cyclopropyl ketones.
Org Biomol Chem
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Department of Material and Chemical Engineering, Zhengzhou University of Light Industry, 136 Science Avenue, 450001, Zhengzhou, Henan Province, P.R. China.
In the present study, the mechanism, origin of chemoselectivity, and substituent effects of the phosphine-catalyzed ring-opening reaction of cyclopropyl ketone have been investigated using the DFT method. Multiple pathways, including the formation of hydrofluorenone, the Cloke-Wilson product, and cyclopenta-fused product, were studied and compared. The computational results show that the pathway for the formation of hydrofluorenone is the most favorable one, which involves four processes: nucleophilic substitution to open the three-membered ring, an intramolecular Michael addition for the formation of an enolate intermediate, an intramolecular [1,5]-proton transfer to give ylide, and an intramolecular Wittig reaction to deliver the final product.
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J Org Chem
November 2024
Department of Chemistry, School of Natural Sciences, The University of Manchester, ManchesterM13 9PL, U.K.
Article Synopsis
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