Living polymerization is a method by which polymers having a narrow molecular weight distribution may be obtained. Block copolymers may also be synthesized using the method. Block copolymers may display improved mechanical andor chemical properties over corresponding random copolymers. One promising method for free radical polymerization with living characteristics is reversible addition-fragmentation chain transfer (RAFT) polymerization. However, known methods for synthesis of the chain transfer agents are unsatisfactory for various reasons, including safety, cost, and sensitivity concerns regarding the use of Grignard reagents, inability to utilize desirable probe functionalities because of incompatibility with reagents, lack of suitable thiol, thioacid andor disulfide precursors, and low yield from the reactions. This invention provides a process for the synthesis of dithiocarboxylic esters that eliminates the use of Grignard reagents, allows for synthesis of functional dithiocarboxylic esters, requires inexpensive and readily available starting materials, and provides high yields.