Stereoselective Amine Addition to Six-Membered Cyclic Nitronates Promoted by Silyl Triflate



Six-membered cyclic nitronates couple with amines or their N-silyl derivatives in a diastereoselective fashion to give 3-amino-substituted nitroso acetals in 53–89 % yield through silyl triflate electrophilic catalysis. Stereodifferentiation of this process is determined by thermodynamic control, which is realized due to reversibility of amine addition and a decreased nitrogen inversion barrier in the resulting nitroso acetals. Selected chemical transformations of nitroso acetals were examined.