A catalytic asymmetric O‐nitroso aldol reaction of alkenyl trifluoroacetates with nitrosoarenes was achieved by using QuinoxP*·AgOAc [(R,R)‐QuinoxP* = (–)‐(R,R)‐2,3‐bis(tert‐butylmethylphosphino)quinoxaline] as the chiral precatalyst and N,N‐diisopropylethylamine as the base precatalyst in the presence of methanol. Optically active α‐aminooxy ketones with up to 99 % ee were regioselectively obtained in moderate to high yields by the in situ generated chiral silver enolates.

A catalytic asymmetric N-nitroso aldol reaction of alkenyl trifluoroacetates with nitrosoarenes was achieved using a DTBM-SEGPHOS·AgOTf complex as the chiral precatalyst and KHMDS as the base precatalyst in the presence of metha-nol. Optically active α-hydroxyamino ketones with up to 89% ee were regioselectively obtained in moderate to high yields not only from acyclic alkenyl esters but also from cyclic ones through the in situ generated chiral silver enolates.