Copper-catalyzed fluoroamide-directed remote benzylic C-H olefination: facile access to internal alkenes

The general, site-selective copper-catalyzed fluoroamide-directed remote benzylic C-H olefination of N-fluoroamides with terminal alkenes for producing internal alkenes is disclosed. This protocol proceeds via a hybrid Cu-radical mechanism, which synergistically combines the favorable features of radical transformations (such as a site-selective remote C-H hydrogen atom transfer (HAT) step) with those of transition-metal catalysis (such as a selective beta-hydrogen elimination step). The cooperative Cu and dinitrogen-based ligand catalytic systems are crucial, as they not only preferentially enable the coupling of terminal alkenes with remote benzylic C-H bonds through the chemoselective recognition of two remote delta-C(sp(3))-H bonds respectively existing in two distinct alkyl-based chains linked to the nitrogen atom of the N-fluoroamides, but they also precisely control site selectivity for the olefination of remote benzylic C-H bonds in a delta position relative to the amidyl nitrogen atom.

Automated summary

This study reveals a novel copper-catalyzed remote benzylic C-H olefination of N-fluoroamides using a Cu-radical mechanism. The reaction combines the advantages of radical transformations and transition-metal catalysis, and utilizes a cooperative Cu and dinitrogen-based ligand catalytic system to achieve site-selectivity around the nitrogen atom.