6-amino[14]aneS(4): A new amine-functionalised crown chalcogenide

We report the first synthesis of 6-amino-1,4,8,11-tetrathiacyclotetradecane (6-amino[14]aneS(4), 1) which is, to our knowledge, the first example of a crown chalcogenide incorporating a primary amine on the carbon backbone. B oth routes discussed herein have as their key step functional group convers ion from hydroxyl to phthalimide-protected amine using the Mitsunobu reacti on. The first route entails Mitsunobu reaction of 6-hydroxy[14]aneS(4) (2) with phthalimide and results in the formation of a mixture of products whos e distribution implies the common intermediacy of an episulfonium ion (EPSI ). In the second pathway, 1,3-dichloro-2-propanol is converted 2-amino-1,3- dichloropropane N-phthalimide (3) from which 6-amino[14]aneS(4) N-phthalimi de (4) can be obtained by cyclisation with 1,4,8,11-tetrathiaundecane under high dilution conditions in DMF in the presence of Cs2CO3. Deprotection of 4 with NH2NH2 hydrate yields the target molecule, 1.