%ALiu, Lei%ALee, Wes%AYuan, Mingbin%AAcha, Chris%AGeherty, Michael%AWilliams, Brandon%AGutierrez, Osvaldo%Anull Ed.%BJournal Name: Chemical Science; Journal Volume: 11; Journal Issue: 12 %D2020%I %JJournal Name: Chemical Science; Journal Volume: 11; Journal Issue: 12 %K %MOSTI ID: 10214127 %PMedium: X %TIntra- and intermolecular Fe-catalyzed dicarbofunctionalization of vinyl cyclopropanes %XDesign and implementation of the first (asymmetric) Fe-catalyzed intra- and intermolecular difunctionalization of vinyl cyclopropanes (VCPs) with alkyl halides and aryl Grignard reagents has been realized via a mechanistically driven approach. Mechanistic studies support the diffusion of alkyl radical intermediates out of the solvent cage to participate in an intra- or intermolecular radical cascade with a range of VCPs followed by re-entering the Fe radical cross-coupling cycle to undergo (stereo)selective C(sp 2 )–C(sp 3 ) bond formation. This work provides a proof-of-concept of the use of vinyl cyclopropanes as synthetically useful 1,5-synthons in Fe-catalyzed conjunctive cross-couplings with alkyl halides and aryl/vinyl Grignard reagents. Overall, we provide new design principles for Fe-mediated radical processes and underscore the potential of using combined computations and experiments to accelerate the development of challenging transformations. %0Journal Article