| Abstract: | An isothiourea‐catalyzed enantioselective Michael addition of aryl ester pronucleophiles to vinyl bis‐sulfones via C(1)‐ammonium enolate intermediates has been developed. This operationally simple method allows the base‐free functionalization of aryl esters to form α‐functionalized products containing two contiguous tertiary stereogenic centres in excellent yield and stereoselectivity (all ≥99:1 er). Key to the success of this methodology is the multifunctional role of the aryloxide, which operates as a leaving group, Brønsted base, Brønsted acid and Lewis base within the catalytic cycle. Comprehensive mechanistic studies, including variable time normalization analysis (VTNA) and isotopologue competition experiments, have been carried out. These studies have identified (i) orders of all reactants; (ii) a turnover‐limiting Michael addition step, (iii) product inhibition, (iv) the catalyst resting state and (v) catalyst deactivation through protonation. |
