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Ir-Catalyzed Atroposelective Desymmetrization of Heterobiaryls: Hydroarylation of Vinyl Ethers and Bicycloalkenes

AuthorsRomero-Arenas, Antonio; Hornillos, Valentín ; Iglesias-Sigüenza, Javier; Fernández, Rosario; López-Serrano, Joaquín ; Ros, Abel ; Lassaletta, José M.
Issue Date2020
PublisherAmerican Chemical Society
CitationJournal of the American Chemical Society 142: 2628- 2639 (2020)
AbstractA highly regio-, diastereo-, and enantioselective, scalable Ir-catalyzed hydroarylation of electron-rich acyclic and tensioned cyclic olefins with heterobiaryls is described. The reaction of acyclic vinyl ethers, dihydrofuran, and norbornenes with a variety of aryl isoquinoline, quinazoline, and picoline derivatives takes place with simultaneous installation of central and axial chirality, reaching complete branched/linear or exo/endo ratios and excellent diastereo- and enantiomeric excesses when in situ formed [Ir/Tol-SDP] or [Ir/Tol-BINAP] complexes are used as the catalysts. Deuterium labeling experiments and a comprehensive computational study suggest that, despite fast double bond migratory insertion into Ir-H, the reaction proceeds through a modified Chalk-Harrod mechanism, starting with selectivity-determining insertion into Ir-C. The regioselectivity is controlled by the electron-donating alkoxy group, whereas diastereo- and enantioselectivity have a complex origin, which depend on the relative orientation of the alkoxy group and the establishment of adequate π-πinteractions between the biaryl and the phosphine.
Publisher version (URL)http://dx.doi.org/10.1021/jacs.9b12858
Identifiersdoi: 10.1021/jacs.9b12858
issn: 1520-5126
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