Copper-Catalyzed sp² C–H Arylation and Alkynylation of Allenes via Hydrogen Atom Abstraction

Abstract

Development of methods for the sp² C-H transformations of allenes has received much attention, and it presents a powerful tool for the synthesis of complicated allene-containing bioactive molecules. With a copper-catalyzed radical relay, sp² allenic C-H arylation and alkynylation were established herein, using various aryl boronic acids and trimethoxysilyl-substituted alkynes as carbon nucleophiles and using electrophilic N-F reagents as nitrogen-centered radical precursors. These methods featured excellent site selectivity to deliver fully substituted allenes efficiently. Moreover, with silyl-substituted allenes as substrates, a subsequent dual sp² C-H functionalization process was established as well, which allowed for the divergent synthesis of multifunctionalized allenes, significantly expanding their chemical spaces.