A Direct Assembly Approach to the Synthesis of N,N'-Bridged Calix[4]pyrroles: The Synthesis of a 1,5-Diazacyclononatriene Locked in a Saddle Conformation

Ring closure of 1,2-bis(1-pyrrolylmethyl)benzene in the acid-catalysed condensation with acetone yields the 1,5-diazacyclononatriene [o-C 6H 4(CH 2NC 4H 3-2) 2C(CH 3) 2] as the sole identifiable product. The twisted or saddle conformation of the 1,5-diazacyclononatriene, which was confirmed by X-ray crystal structure determination, is conformationally rigid in solution. The conformation of the 1,5-diazacyclononatriene prevents the formation of the target N,N′-bridged calix[4]pyrrole by further acid-catalysed condensation with acetone, the reaction affording unidentified oligomers/polymers instead. The acid-catalysed condensation of 1,3- and 1,4-bis(1-pyrrolylmethyl)benzene with acetone also yields unidentified oligomers/polymers. © 2005 Taylor & Francis Group Ltd.