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. Author manuscript; available in PMC: 2023 Sep 7.
Published in final edited form as: Nature. 2020 Jun 1;583(7817):548–553. doi: 10.1038/s41586-020-2399-1

Fig. 5 |. Mechanistic studies support a cation-assisted, turnover-limiting, enantiodetermining and irreversible oxidative addition from a rapidly interconverting mixture of diastereomeric olefin complexes under Curtin–Hammett control.

Fig. 5 |

a, Proposed mechanism. b, NMR spectroscopic characterization of the catalyst resting state. c, Comparison of allylic fluoroalkylation reactions with 3-fluorocinnamyl electrophiles and 3-substituted 3,3-difluoropropenes. d, η1 allyl intermediates are too high in energy to participate. e, Quadrant diagram for Ir(i) olefin complexes. f, Stereochemical model for 3-fluorocinnamyl electrophiles and 3-substituted 3,3-difluoropropenes; see Supplementary Information for a more detailed discussion. OA, oxidative addition; RE, reductive elimination; LS, ligand substitution; TLS, turnover-limiting step; EDS, enantiodetermining step; EXSY, exchange spectroscopy; krel, relative rate constant; ΔGrel, relative Gibbs free energy.