Fluoroamide-Directed Regiodivergent C-Alkylation of Nitroalkanes

Herein, by exploiting different activation modes of fluoroamides,we achieved alpha- and delta-C(sp(3))-H alkylationof nitroalkanes with switchable regioselectivity. Cu catalysis enabledthe interception of a distal C-centered radical by a N-centered radicalto couple nitroalkanes and unactivated delta-C-H bonds. Inaddition, imines generated in situ by fluoroamides were trapped bynitroalkanes to realize the alpha-C-H alkylation of amides.Both of those scalable protocols have broad substrate scopes and goodfunctional group tolerance.

Automated summary

In this study, we achieved alpha- and delta-C(sp(3))-H alkylation of nitroalkanes with switchable regioselectivity by exploiting different activation modes of fluoroamides. Cu catalysis enabled the interception of a distal C-centered radical by a N-centered radical, allowing the coupling of nitroalkanes and unactivated delta-C-H bonds. Additionally, imines generated in situ by fluoroamides were trapped by nitroalkanes to realize the alpha-C-H alkylation of amides. Both of these scalable protocols have broad substrate scopes and good functional group tolerance.