Ruthenium-catalyzed oxidative cyanation of tertiary amines with molecular oxygen or hydrogen peroxide and sodium cyanide: sp3 C-H bond activation and carbon-carbon bond formation.

摘要: Ruthenium-catalyzed oxidative cyanation of tertiary amines with molecular oxygen in the presence sodium cyanide and acetic acid gives corresponding α-aminonitriles, which are highly useful intermediates for organic synthesis. The reaction is first demonstration direct sp3 C−H bond activation α to nitrogen followed by carbon−carbon formation under aerobic oxidation conditions. catalytic seems proceed (i) α-C−H ruthenium catalyst give an iminium ion/ruthenium hydride intermediate, (ii) hydroperoxide, (iii) HCN α-aminonitrile product, H2O2, Ru species, (iv) generation oxoruthenium species from (v) α-aminonitriles. On basis last two pathways, a new type ruthenium-catalyzed H2O2...