Bifunctional organoboron–phosphonium catalysts for coupling reactions of CO 2 and epoxides

and cyclohexene oxide or vinyl cyclohexene oxide to provide polycarbonates with >99% polymer selectivity and carbonate linkages. The coupling reactions of aliphatic epoxides such as PO, having lower energy barrier to cycloaddition formation compared to alicyclic epoxides, preferentially provided cyclic carbonates in good yields. It was demonstrated that these organoboron-phosphonium catalysts are sensitive to chain transfer agents like water, and hence are deactivated in its presence. This is opposite to what is observed for metal based catalysts for these transformations, where water serves as a precursor to the chain-transfer agent diols.