Synthesis and characterization of coronanes: Multicyclopropane-fused macrocyclic arrays

Stepwise macrocyclization of the all syn-trans-1,15-quinquecyclopropanedime thanol (4) with iso- and terephthaloyl chlorides and 4,4'-methanediyl-diben zoic acid (28) gave the corresponding coronanes 22, 23, and 32. The same pr otocol was used with all syn-trans-1,21-septecyclopropanedimethanol (5) and 2,3-naphthalenedicarboxylic acid to obtain the macrolide 27. Direct macroc yclization of diol 4 and 1,10-phenanthroline-2,9-dicarbonyl chloride (33) a nd 2,2'-bipyridine-4,4'-dicarbonyl chloride (35) gave the coronanes 34 and 36, respectively. Ring closing metathesis (RCM) of the diene 42 using Cl-2( Cy3P)(2)Ru=CHPh (48) (Grubbs's catalyst) gave the macrocyclic lactone 45. T he structures of coronanes 22, 23, 32, 34, 36, and 45 were confirmed by X-r ay crystallographic studies which showed the cyclopropyl chain to adopt ver y differing conformations throughout the series. Several of the macrocycles have significant free pathways through their ring centers, and in the case of compound 34 there is a water molecule hydrogen bonded within the ring. This latter compound has the potential to act as a chiral ligand to metal c enters.