A new. general synthesis of the first /?-substituted tetra-and hexaalkyl terpyrroles is described. Also described are two new classes of expanded porphyrins derived from the hexaalkyl terpyrrole. The key step in the terpyrrole formation is the copper(i1)-mediated oxidative coupling of the LDA-derived enolates of a-keto pyrroles. The first new expanded porphyrin reported here, the so-called "orangarin", contains five new class of expanded porphyrins, the pyrrolic subunits and two bridging carbon "arnethyrins", are 24n-electron nonaroatoms, and is formally a 20n-electron matic macrocycles containing six pyrrole nonaromatic macrocycle.