Halodiazoacetates as useful tools for selective halo-functionalization

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. © 2011 IUPAC.