Carbosubstitutions in spirene triflates can be effected by Pd-catalyzed couplings with stannylated or zincated arenes. Differential carbosubstitution resulted from stepwise triflation and coupling in spiro[4,4]nonane-1,6-dione. Catalytic hydrogenation of the 1,6-diphenyl-1,6-diene gave the cic, cis-disubstituted spirane. Metal hydride reduction of intermediate monoketone gave mainly the cis-alcohol. (C) 1999 Elsevier Science Ltd. All rights reserved.