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-M2[RuH2((R,R)-HNCH(Ph)CH(Ph)NH)­((R)-BINAP)], where M = Li+ (8-M′ 2...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2013-06, Vol.135 (23), p.8578-8584
Main Authors: John, Jeremy M, Takebayashi, Satoshi, Dabral, Nupur, Miskolzie, Mark, Bergens, Steven H
Format: Article
Language:English
Subjects:
Alcohols - chemical synthesis
Alcohols - chemistry
Amides - chemistry
Catalysis
Hydrogenation
Imides - chemistry
Ketones - chemistry
Molecular Structure
Organometallic Compounds - chemistry
Ruthenium - chemistry
Stereoisomerism
Temperature
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Summary: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-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.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja401294q