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Hypophosphite adds to alkenes in high yields under solvent-free conditions at elevated temperature, including α,β-unsaturated carboxylates. The reaction proceeds by a radical mediated pathway. Hypophosphite addition is also effective under non-acidic aqueous conditions employing radical initiators. These methods complement other hypophosphite addition reactions and simplify the synthesis of polyfunctional H-phosphinates.The enantioselective reaction of imines bearing a cyano group as an activating group with malonic acid half thioesters