Abstract
Herein we describe the first construction of fluorinated tertiary stereocenters based on an alkene C(sp(2))-C(sp(2)) bond cleavage. The new process, that takes advantage of a Rh-catalyzed carbyne transfer, relies on a branched-selective fluorination of tertiary allyl cations and is distinguished by a wide scope including natural products and drug molecule derivatives as well as adaptability to radiofluorination.