Silver- and gold-catalyzed divergent cascade cycloisomerization/[3 + 2] versus [2 + 2 + 1] cycloaddition towards a stereoselective access to heterohexacyclic derivatives

P NMR analyses. This process, involving the formation of C-C, C-O, and C-N bonds and of three stereogenic centers led to privileged scaffolds in a context of the search for increased molecular diversity of drug-candidate libraries. The versatility of this methodology was demonstrated by the synthesis of 25 different hexacyclic scaffolds (yields up to 98%). Gram-scale synthesis as well as post-functionalization reactions illustrated the versatility and interest of these catalytic transformations. DFT calculations were performed to rationalize the proposed mechanism of this cascade reaction.