Divergent synthesis of pyrrolizine derivatives through C-H bond functionalization of pyrroles.

Presented herein is the synthesis of diversely functionalized pyrrolizines from the reaction of -alkoxycarbamoyl pyrroles with CF-ynones. The formation of the product is based on a C-H bond activation-initiated cascade process including -alkoxycarbamoyl group-directed alkenylation of the pyrrole scaffold followed by simultaneous intramolecular nucleophilic addition along with cleavage and transfer of the directing group. By taking advantage of the rich chemistry of the transferred alkoxycarbamoyl moiety, the products could be transformed into a series of structurally and biologically interesting pyrrolizine derivatives.

Synthesis of CF-Substituted -Heterocyclic Compounds Based on C-H Activation-Initiated Formal [2 + 3] Annulation Featuring with a Latent Nucleophilic Site.

Presented herein is a novel synthesis of CF-substituted pyrrolo[1,2-]indole derivatives based on the cascade reactions of -alkoxycarbamoyl indoles with CF-ynones. Mechanistically, the formation of a product involves a tandem process initiated by Rh(III)-catalyzed and -alkoxycarbamoyl group-directed regioselective C2-H alkenylation of the indole scaffold followed by in situ removal of the directing group and intramolecular -nucleophilic addition/annulation under one set of reaction conditions. To our knowledge, this is the first example in which a -alkoxycarbamoyl unit initially acts as a directing group for C2-H functionalization of the indole scaffold and is then removed to provide the required reactive -moiety for subsequent intramolecular condensation.