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The use of 2-(trimethylsilylethyl)sulfonamide (SES-NH 2 ) has permitted the selective and efficient synthesis of new triolefinic 15-membered azamacrocycles 3. Differential coordination mode with palladium has been observed when macrocycle 3aab [(E,E,E)-1,6-bis(p-tolylsulfonyl)-1,6,11-triazacyclopentadeca-3,8,13-triene] was treated with a palladium(0) or a palladium(II) source.