Equilibrium Shift in Rhodium-catalyzed Synthesis of Organosulfur and Organophosphorus Compounds

Abstract

C-S/C-P bond formation is an essential process for the synthesis of organosulfur and organophosphorus compounds. Recently, we found single-bond metathesis reactions to be useful for such synthesis, and a variety of reactions involving cleavage of heteroatom bonds were developed. Single bond metathesis reactions were often reversible, and therefore the development of the method to control equilibrium turned to be important.
We developed an equilibrium control method using co-substrates. Rhodium-catalyzed method can be used for acyl transfer equilibrium between acid fluorides, acylphosphine sulfides, thioesters, and aryl esters. Appropriate co-substrates changed the relative thermodynamic stabilities of substrates and products, and efficiently provided desired products. This method using the combination of a transition metal catalyst and heteroatom acceptors can be generally used for the synthesis of organoheteroatom compounds.