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Pure Appl. Chem., 2011, Vol. 83, No. 3, pp. 565-575

Published online 2011-01-31

Halodiazoacetates as useful tools for selective halo-functionalization

Hanne Therese Bonge* and Tore Hansen

Department of Chemistry, University of Oslo, Sem Sælands vei 26, N-0315 Oslo, Norway

Abstract: The halodiazoacetates are a group of synthetically useful halogenated diazo compounds that can be used in Rh(II)-catalyzed carbenoid reactions. In the reactions between the halodiazoacetates and electron-rich, sterically unhindered alkenes, halocyclopropanes are formed in good to excellent yields. The halodiazoacetates also react well in C–H and Si–H insertion reactions, broadening the synthetic utility of these reactions. The products of the reactions are synthetically useful α-halocarbonyl compounds. Density functional theory (DFT) calculations have given insight into the mechanism of the cyclopropanation and C–H insertion reactions of the halodiazoacetates, and have also shown that the halodiazoacetates have a particularly high kinetic activity.