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| - A Theoretical Investigation of the Co(CO)4--CatalyzedCarbonylative Ring Expansion of N-Benzoyl-2-methylaziridine toβ-Lactams: Reaction Mechanism and Effect of Substituent at theAziridine Cα Atom
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| - The reaction mechanism of the Co(CO)4--catalyzed carbonylative ring expansion of N-benzoyl-2-methylaziridine to afford N-benzoyl-4-methyl-2-azetidinone and N-benzoyl-3-methyl-2-azetidinone wasinvestigated by using the B3LYP density functional theory methodology in conjunction with the conductorpolarizable continuum model/united atom Kohm−Sham method to take into account solvent effects.Computations predict that the most favorable reaction mechanism differs from the experimental proposalsexcept for the nucleophilic ring-opening step, which is the rate-determining one. The regioselectivityand stereospecificity experimentally observed is explained in terms of the located reaction mechanism.The substitution of the methyl group at the carbon α of aziridine by the phenyl one gives rise to theobtaining of an only product that corresponds to the CO insertion into the C(substituted)−N bond inaccordance with experimental findings. When the ethyl group replaces the methyl one the CO insertionoccurs into the two C−N bonds, but the regioselectivity of the process is higher than that of the methylsubstituent.
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