Ammonium zincates as catalysts for the microwave‐enhanced synthesis of symmetric piperazines by regioselective opening of aziridines

2,5-disubstituted N,N'-alkylpiperazines represent an interesting target in organic synthesis both for pharmaceutical or agrochemical applications and as a promising class of ligands in coordination chemistry. We report here a microwave-enhanced synthesis of these compounds starting from non-activated N-alkyl aziridines in the presence of catalytic amounts of simple ammonium metallates. A remarkable TOF of 2787.9 h-1 has been observed in the case of [TBA]2[ZnI4] as the catalyst (catalyst loading 0.1 mol%) and with an almost complete selectivity (up to 97%) in favor of both diastereoisomers (meso and chiral form) of the target 2,5-disubstituted piperazines, obtained in 1:1 ratio. The two isomers are easily separated, because the meso form precipitates in pure from the reaction crude. A stereochemical investigation and the unprecedented isolation of 2,6-disubstituted N,N'-alkylpiperazines allowed us to shed light on the reaction mechanism.