Asymmetric Catalysis by Architectural and Functional Molecular Engineering: Practical Chemo- and Stereoselective Hydrogenation of Ketones

Noyori, Ryoji; Ohkuma, Takeshi

doi:10.1002/1521-3773(20010105)40:1<40::aid-anie40>3.0.co;2-5

Cited by 1,800 publications

(210 citation statements)

References 359 publications

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“…For this reason, much effort has been made over the last 30 years to develop efficient techniques for asymmetric reduction of prochiral ketones. In particular, asymmetric catalysis provides organic chemists with a unique tool for their efficient synthesis [23], although none of these are, as yet, optimal [24–26]. In recent years, metal-catalyzed hydrosilylation of ketones has been investigated using chiral ligands [27–33], while enantioselective hydrogenation of prochiral ketones to optically active secondary alcohols is among the most fundamental subjects in modern synthetic chemistry.…”

Section: Resultsmentioning

confidence: 99%

Concise methods for the synthesis of chiral polyoxazolines and their application in asymmetric hydrosilylation

Li¹,

Xu²,

Qiu³

2010

Beilstein J. Org. Chem.

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SummarySeven polyoxazoline ligands were synthesized in high yield in a one-pot reaction by heating polycarboxylic acids or their esters and chiral β-amino alcohols under reflux with concomitant removal of water or the alcohol produced in the reaction. The method is much simpler and more efficient in comparison to those methods reported in the literature.The compounds were used as chiral ligands in the rhodium-catalyzed asymmetric hydrosilylation of aromatic ketones, and the effects of the linkers and the substituents present on the oxazoline rings on the yield and enantioselectivity investigated. Compound 2 was identified as the best ligand of this family for the hydrosilylation of aromatic ketones.

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Section: Resultsmentioning

confidence: 99%

Concise methods for the synthesis of chiral polyoxazolines and their application in asymmetric hydrosilylation

Li¹,

Xu²,

Qiu³

2010

Beilstein J. Org. Chem.

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“…The crude product was washed with hexane and dried under reduced pressure. Further purification by column chromatography (with 8:1 CHCl 3 /CH 3…”

Section: Synthesis Of 12-bis(p-hydroxyphenyl)-nnbis(tert-butoxycarbmentioning

confidence: 99%

“…Noyori et al 3 developed an excellent chiral catalyst system effective for the hydrogenation of simple ketones. Aromatic ketones can be smoothly hydrogenated with (S)-BINAP/RuCl 2 complexed with (S,S)-diphenylethylenediamine in the presence of t-BuOK to give the corresponding secondary alcohol in a quantitative yield with a high level of enantioselectivity.…”

Section: Asymmetric Hydrogenation Of Acetophenone With a Polymer-suppmentioning

confidence: 99%

“…For instance, the chiral 1,2-diamine/ RuCl 2 /BINAP 2 system shows powerful catalytic activity in the asymmetric hydrogenation of ketones. 3 Many other examples of catalyst systems containing 1,2-diamine involve those used for epoxidation, 4 Diels-Alder reactions, 5 aldol reac-tions, 6 dihydroxylations of olefins, 7 nucleophilic additions of carbonyls, 8 conjugate additions, 9 protonation of enolates, 10 cyclopropanations, 11 and aziridinations. 12 The addition of a vinylbenzyl group to the chiral 1,2-diamine molecule produces a novel type of chiral diamine monomer that can be copolymerized with other achiral vinyl monomers such as styrene.…”

Section: Introductionmentioning

confidence: 99%

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Preparation of the enantiopure 1,2‐diamine monomer and its polymerization: The efficient polymeric chiral ligand of an asymmetric hydrogenation catalyst

Itsuno

Tsuji

Takahashi

2004

J. Polym. Sci. A Polym. Chem.

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An enantiopure 1,2‐diamine monomer possessing a p‐vinylbenzyl group as a polymerizable group was synthesized from chiral 1,2‐bis(p‐hydroxyphenyl)‐N,N′‐bis(tert‐butoxycarbonyl)‐1,2‐diaminoethane. The chiral monomer was copolymerized with styrene, and this was followed by the deprotection of the tert‐butoxycarbonyl group, which yielded the polymer‐supported chiral 1,2‐diamine. The polymeric catalyst system was established with the polymeric chiral 1,2‐diamine complexed with 2,2′‐bis(diphenylphosphino)‐1,1′‐binaphthyl/RuCl2. In the presence of potassium tert‐butoxide (t‐BuOK), the polymeric catalyst system worked well in the asymmetric hydrogenation of aromatic ketones. The corresponding chiral secondary alcohols were obtained in quantitative yields with a high level of enantioselectivity. The insolubility of the catalyst, caused by the crosslinked structure of the polymer, made it recyclable. The polymeric catalyst was reused several times without a loss of catalytic activity. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4556–4562, 2004

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“…Of these, asymmetric organic synthesis is the most efficient and useful method of producing chiral synthons. Chiral metal catalysts such as BINAP-Ru [1] and chiral Co (II) salen complex [2,3] have been successfully used as chemical catalysts for synthesizing chiral alcohols or chiral diols from various ketones or epoxides in a number of cases. However, trace metal contamination left in the products and the high cost of catalysts are unresolved difficulties affecting many reactions.…”

Section: Introductionmentioning

confidence: 99%

Production of (R)-3-Quinuclidinol by E. coli Biocatalysts Possessing NADH-Dependent 3-Quinuclidinone Reductase (QNR or bacC) from Microbacterium luteolum and Leifsonia Alcohol Dehydrogenase (LSADH)

Isotani

Kurokawa

2012

IJMS

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We found two NADH-dependent reductases (QNR and bacC) in Microbacterium luteolum JCM 9174 (M. luteolum JCM 9174) that can reduce 3-quinuclidinone to optically pure (R)-(−)-3-quinuclidinol. Alcohol dehydrogenase from Leifsonia sp. (LSADH) was combined with these reductases to regenerate NAD+ to NADH in situ in the presence of 2-propanol as a hydrogen donor. The reductase and LSADH genes were efficiently expressed in E. coli cells. A number of constructed E. coli biocatalysts (intact or immobilized) were applied to the resting cell reaction and optimized. Under the optimized conditions, (R)-(−)-3-quinuclidinol was synthesized from 3-quinuclidinone (15% w/v, 939 mM) giving a conversion yield of 100% for immobilized QNR. The optical purity of the (R)-(−)-3-quinuclidinol produced by the enzymatic reactions was >99.9%. Thus, E. coli biocatalysis should be useful for the practical production of the pharmaceutically important intermediate, (R)-(−)-3-quinuclidinol.

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Asymmetric Catalysis by Architectural and Functional Molecular Engineering: Practical Chemo- and Stereoselective Hydrogenation of Ketones

Cited by 1,800 publications

References 359 publications

Concise methods for the synthesis of chiral polyoxazolines and their application in asymmetric hydrosilylation

Concise methods for the synthesis of chiral polyoxazolines and their application in asymmetric hydrosilylation

Preparation of the enantiopure 1,2‐diamine monomer and its polymerization: The efficient polymeric chiral ligand of an asymmetric hydrogenation catalyst

Production of (R)-3-Quinuclidinol by E. coli Biocatalysts Possessing NADH-Dependent 3-Quinuclidinone Reductase (QNR or bacC) from Microbacterium luteolum and Leifsonia Alcohol Dehydrogenase (LSADH)

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