Kinetically and thermodynamically controlled synthesis of tetraoxa[14]metacyclophanes and hexaoxa[16]metacyclophanes

The nucleophilic aromatic substitution of 1,5-difluoro-2,4-dinitrobenzene with 2-propylresorcinol in Et3N/CH3CN produces a mixture of syn and anti conformers of the cyclic tetramer and the cyclic hexamer with a kinetically controlled product distribution. Moreover, the reaction in DMF was catalyzed by CsF to also produce a mixture of these cyclic oligomers. In this case, however, the C-O bond is cleaved by the fluoride ion and the cyclization reaction is reversible; therefore, in the presence of excess CsF, the thermodynamically favored product (syn-isomer of cyclic tetramer) is obtained as the major product. The structures of the two conformational isomers of cyclic tetramers were determined by X-ray crystallography. (c) 2006 Elsevier Ltd. All rights reserved.