TRIQUINANE-DERIVED MACROCYCLIC LACTONES AND A [2]-CATENANE - SYNTHESIS AND CHARACTERIZATION

cis,syn,cis-Triquinane diol 1, with its folded topology, hydrophobic p osterior and inwardly directed endo,endo-hydroxy groups, readily enter s into cyclooligomerization reaction with terephthaloyldichloride 4. A s many as nine cyclic oligomers A-I, with macrocyclic ring size varyin g from 28- to 98-membered, have been isolated and characterized. The c yclic oligomers exhibit interesting spatial relationships through the relative orientation of methylene groups on the central five membered ring of the triquinane moiety. Employing X-ray crystallography and sym metry considerations, in conjunction with NMR data, stereostructures o f dimers 5 and 6, trimers 7 and 8 and tetramers 9-12 could be delineat ed. The crystal packing in the case of 5, 6 and 7 shows some interesti ng motifs and many short C-H...O contacts. From the reaction of 1 and 4, a novel [2]-catenane 16, constituted through aromatic spacers and a bulky triquinane entity, has also been isolated and characterized, th rough the incisive analysis of the mass spectral data. (C) 1998 Publis hed by Elsevier Science Ltd. All rights reserved.