Cyclopropanes from Unsaturated Compounds, Methylene Iodide, and Zinc-Copper Couple

Simmons, H. E.; Cairns, T. L.; Vladuchick, Susan A.; Hoiness, Connie M.


The reaction of the organozinc reagent prepared from methylene iodide and zinc-copper couple with substituted unsaturated compounds has proved to be a versatile and convenient method for the synthesis of cyclopropanes. The synthesis is stereospecific with regard to the stereochemistry of the unsaturated compound and is usually free from serious side reactions; it can be carried out under mild conditions in diethyl and affords cyclopropanes often in good yields. This method can be easily adapted to large-scale preparations. Two useful variations of the cyclopropanation reaction have appeared which involve the same or a similar organozinc intermediate: (1) diazomethane reacts with iodide in ether to form a reagent which converts unsaturated compounds to cyclopropanes; (2) methlyene iodide and diethyl zinc react in ether in the presence of unsaturated compounds to cyclopropanes. Processes are known in which a divalent carbon fragment adds to carbon-carbon double bonds either as a free carbene or as an organometallic complex.