Sequential ATRA/Reductive Cyclopropanation Reactions with a Ruthenium Catalyst in the Presence of Manganese

Atom-transfer radical addition (ATRA) reactions of ethyl trichloroacetate, dichloromalononitrile, or diethyl 2,2-dichloromalonate with olefins followed by dechlorination have provided functionalized cyclopropanes in one step. The RuIII complex [Cp*RuCl2(PPh3)] was used as a catalyst precursor and commercial Mn powder as reducing agent. Reactions with the less activated substrate ethyl dichloroacetate gave ATRA products with high turnover numbers but cyclopropanation was not observed.