A Study of Palladium Catalyzed Intra/Intermolecular Cascade Cross Coupling/Cyclizations Involving Bicyclopropylidene

Abstract

The compounds [3-(2-Bromocyclohex-2-enyloxy) prop-1-ynyl]-tert-butyldimethylsilane 3, [4-(2-bromocyclohex-2-en-1-yloxy)but-2-yn-1-yloxy] tert-butyldimethylsilane 5 and dimethyl 2-(2-bromocyclohex-2-enyl)-2-(3-(tert-butyldimethylsilanyl) prop-2ynyl) malonate 9 were prepared and subjected to palladium-catalyzed intra-intermolecular cascade cross couplings incorporating bicyclopropylidene 10 under two types of conditions. In the presence of Pd(OAc)(2), PPh3 and K2CO3 in acetonitrile at 80 degrees C, the products were indene analogues, cross-conjugated tetraenes 11, 12 and 13, respectively. The corresponding spirocyclopropanated tricycle 16 in dimethylformamide at 110 degrees C was obtained, albeit in low yield (24%), and observed as an equimolar mixture of diastereomers, whereas 14, 15 were not fully isolated.