The synthesis of ¦Ã-sulfanyl malonates was achieved through the addition of thiols to electron deficient cyclopropanes. These reactions are catalyzed by calcium acetylacetonate, Ca(acac)2. A variety of electron rich and electron deficient thiols were added without the need for prior activation or exogenous base. The thiol additions to donor-acceptor cyclopropanes bearing electron-rich and electron-deficient aromatic and heteroaromatic groups proceeded in good to excellent yields.