Gold(I)‐Catalysed Asymmetric Hydroamination of Alkenes: A Silver‐ and Solvent‐Dependent Enantiodivergent Reaction

In the present study, we report the first silver‐dependent enantiodivergent gold‐catalysed reaction. The asymmetric intramolecular hydroamination of alkenes catalysed by the combination of a single chiral binuclear gold(I) chloride complex and silver perchlorate can afford both enantiomers of the products by a simple solvent change from toluene to methanol. Such an enantiodivergent reaction is strictly independent of the reaction temperature or of the nature of the catalyst anion and displays the same first‐order kinetic rate law with respect to substrate concentration in both solvents. Beyond a simple solvent effect the enantioinversion is controlled by gold–silver chloride adducts which occur only in methanol and allow a dual activation of the reagent. While one single gold atom activates the alkene moiety, the other gold atom forms an oxophilic gold–silver chloride adduct which is likely to interact with the carbamate function. By comparison with toluene, which affords (S)‐enantiomer, this proximal and bimetallic activation would allow an opposite stereodifferentiation of the two diastereomeric intermediates during the final protodeauration step and lead therefore to the (R)‐enantiomer. Winning both silver and gold: A selected diphosphine binuclear gold(I) complex efficiently catalyses the asymmetric intramolecular hydroamination of alkenes with high yields and enantioselectivities in mild and wet conditions. Both enantiomers of the products can be obtained through the use of a single chiral gold catalyst. By switching the solvent from toluene to methanol, an oxophilic gold–silver adduct is formed and allows a double activation of the N‐alkenyl reagent.