Umpolung reactivity of allylic phosphonates. A simple route to 3‐aminoalkane‐ and 3‐amino‐1‐alkenylphosphonates (phosphinates and phosphine oxides)

Abstract Dibutyl allylphosphonate can react with palladium chloride to give the dibutyl phosphorylated π‐allylpalladium chloride complex which was found to be able to react with a nucleophile, such as sodium dimethyl malonate, to give a functionalized 1‐alkenyl‐phosphonate. A 1‐acetoxyallylic phosphonate can be regarded as the precursor of a phosphorylated π‐allylic palladium complex in a palladium(O) catalyzed reaction, and the latter reacts with nucleophiles to yield 3‐substituted I‐alkenylphosphonates. The reaction is regioselective. Using this methodology, 3‐aminoalkane‐ and 3‐aminoalkenylphosphonates were synthesized from 1‐acetoxyallylic phosphonates regioselectively.