Enaminone substitutents attached to cyclopentadienes: 3E/3Z stereochemistry of 1-metalla-1,3,5-hexatriene intermediates (M = Cr, W) as a functional criterion for the formation of cyclopentadienes and six-membered heterocycles, respectively.

Reactions of NH-enaminones 2 with [2-(1-cycloalkenyl)ethynyl]carbene complexes 7 (M=W, Cr) gave tetrahydropentalenes, tetrahydroindenes, and hexahydroazulenes 8a-i, in which the NH-enaminone moiety is attached to the cyclopentadiene unit. The reaction involved formation of (3E)-1-metalla-1,3,5-hexatriene intermediates, which underwent pi cyclization faster than 3E/3Z isomerization. Tungsten complexes 12 and 13 were characterized as reaction intermediates. Compounds 8 are potentially bidentate ligands with respect to coordination both of the cyclopentadienyl and the enaminone moieties.