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A DFT Study on the Mechanism of Cyclopropanation via Cu(acac)<sub>2</sub>-Catalyzed Diazo Ester Decomposition

Cihan Özen,Nurcan Ş. Tüzün-2008-08-22-Organometallics
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TL;DRAbstract

The mechanism of the copper(I)-catalyzed olefin cyclopropanation reaction with dimethyl diazomalonate has been extensively investigated using the DFT method at B3LYP/6-31G* and BP86/SDD/6-31G* levels. All the possible pathways leading first to a metal carbene and then to the cyclopropane product have been studied with ethene as a model substrate and their energetics are demonstrated. Then the suggested mechanisms were applied to a real system: namely, 2,2-dimethyl-4,7-dihydro-1,3-dioxepine.

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The mechanism of the copper(I)-catalyzed olefin cyclopropanation reaction with dimethyl diazomalonate has been extensively investigated using the DFT method at B3LYP/6-31G* and BP86/SDD/6-31G* levels. All the possible pathways leading first to a metal carbene and then to the cyclopropane product have been studied with ethene as a model substrate and their energetics are demonstrated. Then the suggested mechanisms were applied to a real system: namely, 2,2-dimethyl-4,7-dihydro-1,3-dioxepine.

Keywords

CyclopropanationChemistryDiazoCarbeneCyclopropaneCatalysisDecompositionMedicinal chemistry

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