Chiral cyclam (1,4,8,11-tetraazacyclotetradecane) derivatives were synthesized stepwise from chiral mono-Boc-1,2-diamines and (dialkyl)malonyl dichloride via open diamide-bis(N-Boc-amino) intermediates (65-91%). Deprotection and ring closure with a second malonyl unit afforded the cyclam tetraamide precursors (80-95%). The new protocol allowed the preparation of the target cyclam derivatives (53-59%) by a final optimized hydride reduction. Both the open tetraamine intermediates and the cyclam derivatives successfully coordinated with AuCl3 to give moderate to excellent yields (50-96%) of the corresponding novel tetra-coordinated N,N,N,N-Au(III) complexes with alternating five- and six-membered chelate rings. The testing of the catalytic ability of the cyclam-based N,N,N,N-Au(III) complexes demonstrated high catalytic activity of some complexes in selected test reactions (full conversion in 1-24 h, 62-97% product yields).
Keywords: Au(III); carboalkoxylation; coordination studies; cyclam derivatives; cyclopropanation.
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