Cu-Catalyzed Three-Component Regio- and Stereoselective 1,5-Difunctionalizations of Unactivated Vinyl Cyclopropanes with Fluoroalkyl Iodides and TMSY (Y = CN, N3, NCS).

A new copper-catalyzed, XAT-enabled, three-component 1,5-difunctionalization of unactivated VCPs with fluoroalkyl iodides and TMSY (Y = CN, N3, NCS) offers an efficient approach to synthesize structurally diverse and stereodefined fluoroalkylated alkenyl nitriles. This transformation features a broad range of substrates, high regioselectivity, and stereoselectivity (40 examples in total with 29 products exhibiting ≥10:1 E/Z selectivity). Mechanistic studies, including DFT calculations, suggest a radical pathway involving a sequential SET/XAT process to produce the key fluoroalkyl radical.