An enaminone-directed benzannulation/macrocyclization approach to cyclophane ring systems.
A straightforward and modular preparative approach to 1,3,5-triaroylbenzene-based functionalized cyclophane ring systems has been developed. The key cyclophane-forming macrocyclization reaction was accomplished during the course of a regioselective cross-benzannulation between bis(aryl ethynyl) ketone and enaminone reactants. Macrocyclic products with ring sizes ranging from 18- to 22-membered were successfully constructed. The composition of the tether connecting the two aryl ethynyl ketone fragments can be easily varied; consequently, this method is suitable for construction of a diverse range of structurally distinct cyclophane products. To illustrate this feature, cyclophanes possessing xylyl, alkyl, di(ethylene triamine), and di(ethylene oxy) bridging units were synthesized in isolated yields of 11-46%. Three new cyclophanes (calixarene-like macrocyles 8 and 9, as well as crownophane 18) were structurally characterized by X-ray diffractometry.
Pigge
F Christopher
FC
Department of Chemistry and Biochemistry, University of Missouri-St. Louis, 8001 Natural Bridge Road, St. Louis, Missouri 63121-4499, USA. piggec@jinx.umsl.edu
Ghasedi
Fatemeh
F
Rath
Nigam P
NP