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

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posted on 12.06.2013, 00:00 authored by Jeremy M. John, Satoshi Takebayashi, Nupur Dabral, Mark Miskolzie, Steven H. Bergens
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-M2[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-d8. Details of the origins of the enantioselection for the desymmetrization of meso-cyclic imides by hydrogenation with 8-K are also described herein.