The synthesis of 1,1-disubstituted alkenes typically involves reactions that lack atom economy such as olefination protocols. The use of various ruthenium complexes to effect the addition of terminal alkynes to alkenes is explored as an atom economical strategy. Two new ruthenium complexes have been discovered that effect this reaction at ambient temperature, cyclopentadienylruthenium (triphenylphosphine) camphorsulfonate and cyclopentadienylruthenium tris(acetonitrile) hexafluorophosphate. Using these complexes as catalysts, reactions proceed at ambient temperature in acetone or DMF, respectively. Regioselectivity favoring the formation of a 1,1-disubstituted over a 1,2-disubstituted alkene typically ranges from 9:1 to >25:1. The reaction demonstrates extraordinary chemoselectivity-even di- and trisubstituted alkenes such as present in the products do not compete with the starting monosubstituted alkene. Free hydroxyl groups as well as silyl and PMB ethers are tolerated as are ketones, esters, and amides. The mechanism of the reaction is believed to invoke formation of a metallacyclopentene. To account for the chemo- and regioselectivity, the initial formation of the metallacycle is believed to be reversible. While formation of the 2,5-disubstituted ruthenacyclopentene, which produces the linear product, is believed to be kinetically preferred, the rate of beta-hydrogen elimination from the 2,4-disubstituted ruthenacyclopentene, which produces the branched product, is believed to be faster. Thus, the competition between the rate of beta-hydrogen elimination and cycloreversion rationalizes the results.