Organocatalytic Asymmetric Synthesis of Carbo- and Oxacyclic Seven-Membered Bridged Biaryls via Nucleophile-Dependent Switchable Domino Processes

We disclose herein a highly diastereo- and enantioselective divergent synthesis of seven-membered biaryl-bridged carbo- and oxacyclic frameworks by utilizing the catalytic ability of bifunctional hydrogen-bonding squaramide organocatalysts. Starting with the same biaryl substrate bearing two distinct acceptor sites and by choosing soft or hard nucleophiles, we readily accessed the dibenzocycloheptanes or 5,7-dihydrodibenzo[c,e]oxepines bearing multiple elements of chirality via a domino 1,4/1,2-addition or 1,2/oxa-Michael addition sequence, respectively.