Intra- and intermolecular Fe-catalyzed dicarbofunctionalization of vinyl cyclopropanes. Issue 12 (27th February 2020)

• Record Type: Journal Article
• Authors: Liu, Lei; Lee, Wes; Yuan, Mingbin; Acha, Chris; Geherty, Michael B.; Williams, Brandon; Gutierrez, Osvaldo
• Is Part Of: Chemical science. Volume 11:Issue 12(2020)
• Page Start: 3146
• Page End: 3151
• Publication Date: 2020-02-27
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/d0sc00467g
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : Design 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. Abstract : Design 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.