Transition-Metal-Catalyzed Alkylation of Polyfluoroarenes through C–F Bond Cleavage

Abstract

The polyfluoroarenes are subfields of organofluorines and widely utilized in both medicinal chemistry and materials science. Herein, we briefly summarize the recent advance in the realm of synthesis of these important compounds, with particular attention to our recent CuH-catalyzed defluorinative alkylation of ployfluoroarenes with alkenes through a high site C–F bond cleavage fashion. 1. Introduction 2. Transition-Metal-Catalyzed Alkylation via Selective C–F Bond Cleavage 3. CuH-Catalyzed Defluorinative Alkylation of Polyfluoroarenes with Alkenes 4. Summary and Outlook

Copper-Catalyzed Defluorinative Boroarylation of Alkenes with Polyfluoroarenes

“…Moreover, when a 1:1:1 mixture of 1a , electron-donating group-substituted pentafluorobenzene, and amide-substituted pentafluorobenzene reacted under the optimized conditions, almost only 3a was obtained (Scheme C), suggesting the electron-deficient polyfluoroarene possessed a high reactivity profile. These competitive experiments in combination with previous studies , provided positive evidence that this defluorinative boroarylation might undergo an S N Ar pathway. Moreover, a Hammett study was implemented to explore the electronic effects of the substrate alkene on the reaction rate (Supporting Information).…”

“…Despite these significant advances, the catalytic defluorinative boroarylation of alkenes has remained elusive, partly due to the aforementioned challenges in the territory of C Ar –F bond functionalization. Recently, we have successfully developed a copper-catalyzed defluorinative hydroarylation of alkenes with polyfluoroarenes via the S N Ar pathway under mild conditions . This approach showcased some prominent advantages: (1) excellent regioselectivity, (2) no requirement of stoichiometric quantities of organometallics, and (3) very mild reaction conditions.…”