A New and Versatile Access to Polyazamacroheterocycles and Cryptands Through Ring-Closing Bis(hydroaminomethylation)

The RhI-catalyzed hydroformylation of dienes in the presence of primary amines or secondary α,ω-diamines has been applied to macroheterocyclic ring synthesis. Starting from (hetero)diallylic systems, 12- to 36-membered polyheterocycles have been readily obtained in up to 56% yield. In addition, we show that the macrocyclic systems thus obtained can be debenzylated and that the resulting macrocyclic diamines undergo a second ring-closing bis(hydroaminomethylation) to give cryptand systems.