Base-Catalyzed Bifunctional Addition to Amides and Imides at Low Temperature. A New Pathway for Carbonyl Hydrogenation

Mono- or dideprotonation at the N-H groups of the Noyori ketone hydrogenation catalyst trans-[RuH2((R)-BINAP)((R,R)-dpen)] (1a) yields trans-M[RuH2((R,R)HNCH(Ph)CH(Ph)NH2)((R)-BINAP)], where M = K+ (8-K) or Li+ (8-Li), or trans-M-2[RuH2((R,R)-HNCH(Ph)-CH(Ph)NH)((R)-BINAP)], where M = Li+ (8-M-2'), which have unprecedented activity toward the hydrogenation of amide and imide carbonyls at low temperatures in THF-d(8). Details of the origins of the enantioselection for the desymmetrization of meso-cyclic imides by hydrogenation with 8-K are also described herein.