Enantioselective Transfer Hydrogenation Of Ketones Research Articles

Front Cover Picture: Iridium‐Catalyzed Enantioselective Transfer Hydrogenation of Ketones Controlled by Alcohol Hydrogen‐Bonding and sp3‐C−H Noncovalent Interactions (Adv. Synth. Catal. 21/2020)

Front Cover Picture: Iridium‐Catalyzed Enantioselective Transfer Hydrogenation of Ketones Controlled by Alcohol Hydrogen‐Bonding and <i>sp</i>³‐C−H Noncovalent Interactions (Adv. Synth. Catal. 21/2020)

Iridium‐Catalyzed Enantioselective Transfer Hydrogenation of Ketones Controlled by Alcohol Hydrogen‐Bonding and sp3‐C−H Noncovalent Interactions

AbstractIridium‐catalyzed enantioselective transfer hydrogenation of ketones with formic acid was developed using a prolinol‐phosphine chiral ligand. Cooperative action of the iridium atom and the ligand through alcohol‐alkoxide interconversion is crucial to facilitate the transfer hydrogenation. Various ketones including alkyl aryl ketones, ketoesters, and an aryl heteroaryl ketone were competent substrates. An attractive feature of this catalysis is efficient discrimination between the alkyl and aryl substituents of the ketones, promoting hydrogenation with the identical sense of enantioselection regardless of steric demand of the alkyl substituent and thus resulting in a rare case of highly enantioselective transfer hydrogenation of tert‐alkyl aryl ketones. Quantum chemical calculations revealed that the sp3‐C−H/π interaction between an sp3‐C−H bond of the prolinol‐phosphine ligand and the aryl substituent of the ketone is crucial for the enantioselection in combination with O−H⋅⋅⋅O/sp3‐C−H⋅⋅⋅O two‐point hydrogen‐bonding between the chiral ligand and carbonyl group.magnified image

New functional chiral P-based ligands and application in ruthenium-catalyzed enantioselective transfer hydrogenation of ketones

Metal-catalyzed asymmetric transfer hydrogenation is a powerful and practical method for the reduction of ketones to produce the corresponding secondary alcohols, which are valuable building blocks in the pharmaceutical, perfume, and agrochemical industries. Hence, a series of novel chiral β-amino alcohols were synthesized by chiral amines with regioselective ring opening of (S)-propylene oxide or reaction with (S)-(+)-2-hydroxypropyl p-toluenesulfonate by a straightforward method. The chiral ruthenium catalytic systems generated from [Ru(arene)(μ-Cl)Cl]2 complexes and chiral phosphinite ligands based on amino alcohol derivatives were employed in asymmetric transfer hydrogenation of ketones to give the corresponding optically active alcohols; (2S)-1-{[(2S)-2-[(diphenylphosphanyl)oxy]propyl][(1R)-1-phenylethyl]amino}propan-2-yldiphenylphosphinitobis[dichol-oro(η6-benzene)ruthenium(II)] acts an excellent catalyst in the reduction of α-naphthyl methyl ketone, giving the corresponding alcohol with up to 99% ee. The substituents on the backbone of the ligands were found to have a remarkable effect on both the conversion and enantioselectivity of the catalysts. Furthermore, this transfer hydrogenation is characterized by low reversibility under these conditions.

Enantioselective Transfer Hydrogenation of Ketones Catalyzed by a Manganese Complex Containing an Unsymmetrical Chiral PNP′ Tridentate Ligand

AbstractManganese complexes of the types [Mn(PNP′)(Br)(CO)2] and [Mn(PNP′)(H)(CO)2] containing a tridentate ligand with a planar chiral ferrocene and a centro chiral aliphatic unit were synthesized, characterized, and tested in the enantioselective transfer hydrogenations of 13 ketones. The catalytic reactions proceeded with conversions up to 96 % and ee values up to 86 %. The absolute configuration of all products was determined to be (S). Notably, the presence of dihydrogen (up to 20 bar) did not affect the reduction. On the basis of DFT calculations, preliminary mechanistic details including the origin of the (S) selectivity are presented. The molecular structure of [Mn(PNP′)(Br)(CO)2] was studied by X‐ray diffraction.

ChemInform Abstract: Chiral‐at‐Metal Iridium Complex for Efficient Enantioselective Transfer Hydrogenation of Ketones.

A bis-cyclometalated iridium(III) complex with metal-centered chirality catalyzes the enantioselective transfer hydrogenation of ketones with high enantioselectivities at low catalyst loadings down to 0.002 mol%. Importantly, the rate of catalysis and enantioselectivity are markedly improved in the presence of a pyrazole co-ligand. The reaction is proposed to proceed via an iridium-hydride intermediate exploiting metal-ligand cooperativity (bifunctional catalysis).

ChemInform Abstract: Highly Enantioselective Transfer Hydrogenation of Ketones with Chiral (NH)2P2 Macrocyclic Iron(II) Complexes.

AbstractSeveral iron complexes are presented with the pictured compound FEC being one of the most promising catalysts for the title reaction.

ChemInform Abstract: Isonitrile Iron(II) Complexes with Chiral N2P2 Macrocycles in the Enantioselective Transfer Hydrogenation of Ketones.

Bis(isonitrile) iron(II) complexes bearing a C2-symmetric N2P2 macrocyclic ligand, which are easily prepared from the corresponding bis(acetonitrile) analogue, catalyze the asymmetric transfer hydrogenation (ATH) of a broad scope of ketones in excellent yields (up to 98%) and with high enantioselectivity (up to 91% ee).

Highly Enantioselective Transfer Hydrogenation of Ketones with Chiral (NH)2P2 Macrocyclic Iron(II) Complexes

AbstractBis(isonitrile) iron(II) complexes bearing a C2‐symmetric diamino (NH)2P2 macrocyclic ligand efficiently catalyze the hydrogenation of polar bonds of a broad scope of substrates (ketones, enones, and imines) in high yield (up to 99.5 %), excellent enantioselectivity (up to 99 % ee), and with low catalyst loading (generally 0.1 mol %). The catalyst can be easily tuned by modifying the substituents of the isonitrile ligand.

Highly enantioselective transfer hydrogenation of ketones with chiral (NH)2 P2 macrocyclic iron(II) complexes.

Bis(isonitrile) iron(II) complexes bearing a C2 -symmetric diamino (NH)2 P2 macrocyclic ligand efficiently catalyze the hydrogenation of polar bonds of a broad scope of substrates (ketones, enones, and imines) in high yield (up to 99.5 %), excellent enantioselectivity (up to 99 % ee), and with low catalyst loading (generally 0.1 mol %). The catalyst can be easily tuned by modifying the substituents of the isonitrile ligand.

Isonitrile iron(II) complexes with chiral N2P2 macrocycles in the enantioselective transfer hydrogenation of ketones.

Bis(isonitrile) iron(II) complexes bearing a C2-symmetric N2P2 macrocyclic ligand, which are easily prepared from the corresponding bis(acetonitrile) analogue, catalyze the asymmetric transfer hydrogenation (ATH) of a broad scope of ketones in excellent yields (up to 98%) and with high enantioselectivity (up to 91% ee).

ChemInform Abstract: Biphasic Glycerol/2‐MeTHF, Ruthenium‐Catalyzed Enantioselective Transfer Hydrogenation of Ketones Using Sodium Hypophosphite as Hydrogen Donor.

ChemInformVolume 45, Issue 3 Isocyclic Compounds ChemInform Abstract: Biphasic Glycerol/2-MeTHF, Ruthenium-Catalyzed Enantioselective Transfer Hydrogenation of Ketones Using Sodium Hypophosphite as Hydrogen Donor. Carole Guyon, Carole Guyon Inst. Chim. Biochem. Mol. Supramol., Equipe Catal. Synth. Evironm., Univ. Claude Bernard Lyon, F-69622 Villeurbanne, Fr.Search for more papers by this authorEstelle Metay, Estelle Metay Inst. Chim. Biochem. Mol. Supramol., Equipe Catal. Synth. Evironm., Univ. Claude Bernard Lyon, F-69622 Villeurbanne, Fr.Search for more papers by this authorNicolas Duguet, Nicolas Duguet Inst. Chim. Biochem. Mol. Supramol., Equipe Catal. Synth. Evironm., Univ. Claude Bernard Lyon, F-69622 Villeurbanne, Fr.Search for more papers by this authorMarc Lemaire, Marc Lemaire Inst. Chim. Biochem. Mol. Supramol., Equipe Catal. Synth. Evironm., Univ. Claude Bernard Lyon, F-69622 Villeurbanne, Fr.Search for more papers by this author Carole Guyon, Carole Guyon Inst. Chim. Biochem. Mol. Supramol., Equipe Catal. Synth. Evironm., Univ. Claude Bernard Lyon, F-69622 Villeurbanne, Fr.Search for more papers by this authorEstelle Metay, Estelle Metay Inst. Chim. Biochem. Mol. Supramol., Equipe Catal. Synth. Evironm., Univ. Claude Bernard Lyon, F-69622 Villeurbanne, Fr.Search for more papers by this authorNicolas Duguet, Nicolas Duguet Inst. Chim. Biochem. Mol. Supramol., Equipe Catal. Synth. Evironm., Univ. Claude Bernard Lyon, F-69622 Villeurbanne, Fr.Search for more papers by this authorMarc Lemaire, Marc Lemaire Inst. Chim. Biochem. Mol. Supramol., Equipe Catal. Synth. Evironm., Univ. Claude Bernard Lyon, F-69622 Villeurbanne, Fr.Search for more papers by this author First published: 02 January 2014 https://doi.org/10.1002/chin.201403071Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume45, Issue3January 21, 2014 RelatedInformation

Biphasic Glycerol/2‐MeTHF, Ruthenium‐Catalysed Enantioselective Transfer Hydrogenation of Ketones Using Sodium Hypophosphite as Hydrogen Donor

AbstractSodium hypophosphite has been used as an efficient hydrogen donor in the transfer hydrogenation of aliphatic and aromatic ketones in the presence of [RuCl2(p‐cymene)]2 and 2,2′‐bipyridine in water. The corresponding alcohols were isolated in moderate to excellent yields (39–95 %). Good chemoselectivity was observed with ester, nitrile and halide functionalities in the ketones not being reduced. An enantioselective version of the reaction using [RuCl(p‐cymene){(R,R)‐TsDPEN}] as catalyst in a glycerol/2‐MeTHF biphasic solvent mixture has been developed and allowed the reduction of (hetero)aromatic ketones with excellent chemo‐ and enantioselectivities (up to 97 % ee).

ChemInform Abstract: Synthesis of Novel Chiral Tetraaza Ligands and Their Application in Enantioselective Transfer Hydrogenation of Ketones.

AbstractOnly derivative (Ia) shows some efficiency to produce the alcohols with low to moderate e.e.

Synthesis of novel chiral tetraaza ligands and their application in enantioselective transfer hydrogenation of ketones

National Natural Science Foundation of China [20423002, 20923004, 21173176]; Program for Changjiang Scholars and Innovative Research Team in University [IRT1036]; State Key Laboratory of Physical Chemistry of Solid Surfaces

ChemInform Abstract: Synthesis of Novel Amino Acid Derived Sulfinamides and Their Evaluation as Ligands for the Enantioselective Transfer Hydrogenation of Ketones.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Highly Productive CNN Pincer Ruthenium Catalysts for the Asymmetric Reduction of Alkyl Aryl Ketones

Chiral pincer ruthenium complexes of formula [RuCl(CNN)(Josiphos)] (2-7; Josiphos = 1-[1-(dicyclohexylphosphano)ethyl]-2-(diarylphosphano)ferrocene) have been prepared by treating [RuCl(2)(PPh(3))(3)] with (S,R)-Josiphos diphosphanes and 1-substituted-1-(6-arylpyridin-2-yl)methanamines (HCNN; substituent = H (1 a), Me (1 b), and tBu (1 c)) with NEt(3). By using 1 b and 1 c as a racemic mixture, complexes 4-7 were obtained through a diastereoselective synthesis promoted by acetic acid. These pincer complexes, which display correctly matched chiral PP and CNN ligands, are remarkably active catalysts for the asymmetric reduction of alkyl aryl ketones in basic alcohol media by both transfer hydrogenation (TH) and hydrogenation (HY), achieving enantioselectivities of up to 99 %. In 2-propanol, the enantioselective TH of ketones was accomplished by using a catalyst loading as low as 0.002 mol % and afforded a turnover frequency (TOF) of 10(5)-10(6) h(-1) (60 and 82 degrees C). In methanol/ethanol mixtures, the CNN pincer complexes catalyzed the asymmetric HY of ketones with H(2) (5 atm) at 0.01 mol % relative to the complex with a TOF of approximately 10(4) h(-1) at 40 degrees C.

Synthesis of Novel Amino‐Acid‐Derived Sulfinamides and Their Evaluation as Ligands for the Enantioselective Transfer Hydrogenation of Ketones

AbstractNovel chiral mono‐sulfinyl diamines bearing a stereogenic sulfur atom were prepared in moderate to good yields starting from amino acids by means of a reductive amination of the corresponding amino aldehydes. Their potential as ligands for asymmetric catalysis was evaluated in the metal‐catalyzed enantioselective transfer hydrogenation of alkyl‐aryl ketones. The catalysts were generated in situ from sulfinamides 1a–i and arene complexes of rhodium and ruthenium, and the catalytic reductions led to the formation of chiral alcohols with up to 91 % ee. (© Wiley‐VCH Verlag GmbH &amp; Co. KGaA, 69451 Weinheim, Germany, 2008)

Enantioselective transfer hydrogenation of ketones with planar chiral ruthenocene-based phosphinooxazoline ligands

1,2-Disubstituted planar chiral ruthenocene-based phosphinooxazoline ligands (Rc-PHOX, 3 and 4) were synthesized easily and applied in the transfer hydrogenation of ketones to chiral alcohols using 2-propanol as a source of hydrogen with excellent enantioselectivity and high catalytic activity.

Rhodium-catalyzed asymmetric transfer hydrogenation of alkyl and aryl ketones in aqueous media

A novel lipophilic rhodium catalyst was evaluated in the enantioselective transfer hydrogenation of ketones in water using sodium formate as the hydride donor, and in the presence of sodium docecylsulfonate. Alkyl alkyl ketones were reduced in good yields and in moderate to good enantioselectivities, and the reduction of aryl alkyl ketones proceeded with excellent enantioselectivity (up to 97% ee).

The Importance of Alkali Cations in the [{RuCl2(p‐cymene)}2]–Pseudo‐dipeptide‐Catalyzed Enantioselective Transfer Hydrogenation of Ketones

In the Full Paper by Adolfsson and co-workers, the structure of ligand 4 presented in Figure 1 was incorrect. The correct structure of ligand 4 is shown below. The authors apologize for this error.1