Hydrogenation is a core technology in chemical synthesis. High rates and selectivities are attainable only by the coordination of structurally well-designed catalysts suitable reaction conditions. The newly devised [RuCl(2)(phosphane)(2)(1,2-diamine)] complexes excellent precatalysts for homogeneous hydrogenation simple ketones which lack any functionality capable interacting with metal center. This catalyst system allows preferential reduction C=O function over coexisting C=C linkage...

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAsymmetric hydrogenation of .beta.-keto carboxylic esters. A practical, purely chemical access to .beta.-hydroxy esters in high enantiomeric purityRyoji Noyori, Takeshi Ohkuma, Masato Kitamura, Hidemasa Takaya, Noboru Sayo, Hidenori Kumobayashi, and Susumu AkutagawaCite this: J. Am. Chem. Soc. 1987, 109, 19, 5856–5858Publication Date (Print):September 1, 1987Publication History Published online1 May 2002Published inissue 1 September...

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTPractical Enantioselective Hydrogenation of Aromatic KetonesTakeshi Ohkuma, Hirohito Ooka, Shohei Hashiguchi, Takao Ikariya, and Ryoji NoyoriCite this: J. Am. Chem. Soc. 1995, 117, 9, 2675–2676Publication Date (Print):March 1, 1995Publication History Published online1 May 2002Published inissue 1 March 1995https://pubs.acs.org/doi/10.1021/ja00114a043https://doi.org/10.1021/ja00114a043research-articleACS PublicationsRequest reuse permissionsArticle...

A turnover number (TON) of 2 400 000 and a frequency (TOF) 63 s-1 are achieved with the chiral RuII complex 1 (R=p-CH3 C6 H4 ) in asymmetric hydrogenation acetophenone. Carbonyl-selective α,β-unsaturated ketones proceeds presence these catalysts, 4-substituted cyclohexanones selectively converted into cis alcohols.

Asymmetric hydrogenation of acetophenone with trans-RuH(eta(1)-BH(4))[(S)-tolbinap][(S,S)-dpen] (TolBINAP = 2,2'-bis(di-4-tolylphosphino)-1,1'-binaphthyl; DPEN 1,2-diphenylethylenediamine) in 2-propanol gives (R)-phenylethanol 82% ee. The reaction proceeds smoothly even at an atmospheric pressure H(2) room temperature and is further accelerated by addition alkaline base or a strong organic base. Most importantly, the rate initially increased to great extent increase molarity but subsequently...

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTHomogeneous asymmetric hydrogenation of functionalized ketonesMasato. Kitamura, Takeshi. Ohkuma, Shinichi. Inoue, Noboru. Sayo, Hidenori. Kumobayashi, Susumu. Akutagawa, Tetsuo. Ohta, Hidemasa. Takaya, and Ryoji. NoyoriCite this: J. Am. Chem. Soc. 1988, 110, 2, 629–631Publication Date (Print):January 1, 1988Publication History Published online1 May 2002Published inissue 1 January...

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTStereoselective hydrogenation via dynamic kinetic resolutionR. Noyori, T. Ikeda, Ohkuma, M. Widhalm, Kitamura, H. Takaya, S. Akutagawa, N. Sayo, Saito, Taketomi, and KumobayashiCite this: J. Am. Chem. Soc. 1989, 111, 25, 9134–9135Publication Date (Print):December 1, 1989Publication History Published online1 May 2002Published inissue 1 December 1989https://pubs.acs.org/doi/10.1021/ja00207a038https://doi.org/10.1021/ja00207a038research-articleACS...

Die Hydrierung ist eines der Schlüsselverfahren chemischen Synthese. Hohe Reaktionsgeschwindigkeiten und Selektivitäten sind hierbei lediglich durch die Kombination von strukturell definierten Katalysatoren mit geeigneten Reaktionsbedingungen zu erreichen. Für homogene nichtfunktionalisierten Ketonen, keinerlei zur Koordination an das Metallzentrum befähigte funktionelle Gruppen aufweisen, haben sich uns beschriebenen Rutheniumkomplexe allgemeinen Formel [RuCl2(phosphan)2(1,2-diamin)] als...

ADVERTISEMENT RETURN TO ISSUEPREVCommunicationNEXTAsymmetric Hydrogenation of Alkenyl, Cyclopropyl, and Aryl Ketones. RuCl2(xylbinap)(1,2-diamine) as a Precatalyst Exhibiting Wide ScopeTakeshi Ohkuma, Masatoshi Koizumi, Henri Doucet, Trang Pham, Masami Kozawa, Kunihiko Murata, Eiji Katayama, Tohru Yokozawa, Takao Ikariya, Ryoji NoyoriView Author Information Department Chemistry Research Center for Materials Science, Nagoya University Chikusa, 464-8602, Japan ERATO Molecular Catalysis Project...

ADVERTISEMENT RETURN TO ISSUEPREVArticlePreferential hydrogenation of aldehydes and ketones.Takeshi Ohkuma, Hirohito Ooka, Takao Ikariya, Ryoji NoyoriCite this: J. Am. Chem. Soc. 1995, 117, 41, 10417–10418Publication Date (Print):October 1, 1995Publication History Published online1 May 2002Published inissue 1 October 1995https://doi.org/10.1021/ja00146a041RIGHTS & PERMISSIONSArticle Views4678Altmetric-Citations321LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum full text...

Chiral eta6-arene/N-tosylethylenediamine-Ru(II) complexes, known as excellent catalysts for asymmetric transfer hydrogenation of aromatic ketones in basic 2-propanol, can be used using H2 gas. Active are generated from RuCl[(S,S)-TsNCH(C6H5)CH(C6H5)NH2](eta6-p-cymene) methanol, but not or by combination Ru[(S,S)-TsNCH(C6H5)CH(C6H5)NH](eta6-p-cymene) and CF3SO3H other non-nucleophilic acids. This method allows, the first time, simple under acidic conditions. Hydrogenation base-sensitive...

Catalytic asymmetric cyanations of prochiral unsaturated compounds affording the corresponding nitrile products in high enantiomeric excess (≥90% general) are summarized this review. The nucleophilic cyanide addition onto aldehydes, ketones, and imines is promoted by chiral metal complexes organocatalysts. Recent progress conjugate cyanation α,β-unsaturated carbonyl also discussed. unactivated alkenes catalyzed transition-metal complexes. Current topics intramolecular carbocyanation...

Reaction of a chiral RuCl2(diphosphine)(1,2-diamine) complex and NaBH4 forms trans-RuH(eta1-BH4)(diphosphine)(1,2-diamine) quantitatively. The TolBINAP/DPEN Ru has been characterized by single crystal X-ray analysis as well NMR IR spectra. new complexes allow for asymmetric hydrogenation simple ketones in 2-propanol without an additional strong base. Various base-sensitive are convertible to alcohols high enantiomeric purity with substrate/catalyst ratio up 100 000 under mild conditions....

Asymmetric hydrogenation uses inexpensive, clean hydrogen gas and a very small amount of chiral molecular catalyst, providing the most powerful way to produce wide array enantio-enriched compounds in large quantity without forming any waste. The recent revolutionary advances this field have entirely changed synthetic approach producing performance chemicals that require high degree structural precision. means developing efficient asymmetric hydrogenations is discussed from mechanistic point view.

Stereomutation of a BIPHEP/RuCl2/diamine complex (shown schematically) is possible because the conformational flexibilty BIPHEP ligands. The result an asymmetric activation in Ru-catalyzed hydrogenation carbonyl compounds to optically active alcohols. Whereas racemic BINAP/RuCl2 with chiral diamine activator gives 1:1 mixture two diastereomers, unequal amounts diastereomers can be produced from BIPHEP/RuCl2 and diamine. Ar=3,5-dimethylphenyl,...

ADVERTISEMENT RETURN TO ISSUEPREVCommunicationNEXTAsymmetric Hydrogenation of Amino Ketones Using Chiral RuCl2(diphophine)(1,2-diamine) ComplexesTakeshi Ohkuma, Dai Ishii, Hiroshi Takeno, and Ryoji NoyoriView Author Information Department Chemistry Research Center for Materials Science Nagoya University, Chikusa, 464-8602, Japan Cite this: J. Am. Chem. Soc. 2000, 122, 27, 6510–6511Publication Date (Web):June 24, 2000Publication History Received29 March 2000Published online24 June inissue 1...

A combined system of RuCl2(tolbinap)(pica) and an alkaline or organic phosphazene base catalyzes asymmetric hydrogenation sterically congested tert-alkyl ketones (TolBINAP = 2,2'-bis(di-4-tolylphosphino)-1,1'-binaphthyl, PICA alpha-picolylamine). Hydrogenation with RuH(eta1-BH4)(tolbinap)(pica) does not require any strong base. Alcoholic solvents strongly affect the catalytic efficiency. The reaction proceeds smoothly in ethanol under 1-20 atm H2 at room temperature a substrate to catalyst...

ADVERTISEMENT RETURN TO ISSUEPREVCommunicationNEXTAsymmetric Activation of Racemic Ruthenium(II) Complexes for Enantioselective HydrogenationTakeshi Ohkuma, Henri Doucet, Trang Pham, Koichi Mikami, Toshinobu Korenaga, Masahiro Terada, and Ryoji NoyoriView Author Information Department Chemistry Molecular Chirality Research Unit, Nagoya University, Chikusa, 464-8602, Japan Chemical Technology, Tokyo Institute Meguro, 152, Cite this: J. Am. Chem. Soc. 1998, 120, 5, 1086–1087Publication Date...

Asymmetric hydrogenation of various α-chloro aromatic ketones with Ru(OTf)(TsDPEN)(η6-arene) (TsDPEN = N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine) produces the chiral chlorohydrins in up to 98% ee. This reaction can be conducted even on a 206-g scale. The an ketone phenol moiety has been utilized for synthesis (R)-norphenylephrine without protection−deprotection operations.

A novel ruthenabicyclic complex with base shows excellent catalytic activity in the asymmetric hydrogenation of ketones. The turnover frequency acetophenone reaches about 35,000 min(-1) best case, affording 1-phenylethanol >99% ee. Several aliphatic and base-labile ketones are smoothly converted to corresponding alcohols high enantioselectivity. cycle for this hydrogenation, which structure catalyst is maintained, proposed on basis deuteration experiment spectroscopic analysis data.

[reaction: see text] trans-RuCl2[P(C6H4-4-CH3)3]2(NH2CH2CH2NH2) acts as a highly effective precatalyst for the hydrogenation of variety benzophenone derivatives to benzhydrols that proceeds smoothly at 8 atm and 23-35 degrees C in 2-propanol containing t-C4H9OK with substrate/catalyst ratio 2000-20000. Use BINAP/chiral diamine Ru complex effects asymmetric various ortho-substituted benzophenones benzoylferrocene chiral diarylmethanols consistently high ee.

trans-RuCl(2)[(R)-xylbinap][(R)-daipen] or the S,S complex acts as an efficient catalyst for asymmetric hydrogenation of hetero-aromatic ketones. The proceeds with a substrate-to-catalyst molar ratio 1000-40000 to give chiral alcohols in high ee and yield. enantioselectivity appears be little affected by properties ring. This method allows synthesis duloxetine, inhibitor serotonin norepinephrine uptake carriers.

Chiral arene-N-tosylethylenediamine-Ru(II) complexes can be made to effect both asymmetric transfer hydrogenation and of simple ketones through a slight functional modification by switching reaction conditions. [Ru(OSO2CF3){(S,S)-TsNCH(C6H5)CH(C6H5)NH2}(eta(6)-p-cymene)] catalyzes the acetophenone in methanol afford (S)-1-phenylethanol with 96% ee 100% yield. Like catalyzed similar Ru catalysts basic 2-propanol or formic acid/triethylamine mixture, this proceeds metal-ligand bifunctional...