Mechanism of the Rhodium Porphyrin-Catalyzed Cyclopropanation of Alkenes

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Science  12 Jun 1992:
Vol. 256, Issue 5063, pp. 1544-1547
DOI: 10.1126/science.256.5063.1544


The rhodium porphyrin-catalyzed cyclopropanation of alkenes by ethyl diazoacetate (EDA) is representative of a number of metal-mediated cyclopropanation reactions used widely in organic synthesis. The active intermediate in these reactions is thought to be a metal carbene complex, but evidence for the involvement of metal-olefin π complexes has also been presented. Low-temperature infrared and nuclear magnetic resonance spectroscopies have been used to characterize a rhodium porphyrin-diazoalkyl adduct that results from the stoichiometric condensation of the catalyst and EDA. Optical spectroscopy suggests that this complex is the dominant steady-state species in the catalytic reaction. This compound decomposes thermally to provide cyclopropanes in the presence of styrene, suggesting that the carbene is indeed the active intermediate. Metal-alkene π complexes have also been detected spectroscopically. Kinetic studies suggest that they mediate the rate of carbene formation from the diazoalkyl complex but are not attacked directly by EDA.