Efficient Catalysts For Asymmetric Hydrogenation Research Articles

Nickel-Catalyzed Highly Enantioselective Hydrogenation of β-Acetylamino Vinylsulfones: Access to Chiral β-Amido Sulfones.

The nickel/( S)-Binapine complex was found to be an efficient catalyst for asymmetric hydrogenation of β-acetylamino vinylsulfones to afford chiral β-Amido sulfones with excellent yields and enantioselectivities (up to 95% yields and >99% ee). This protocol has good compatibility with a series of substituted ( Z)-β-acetylamino vinylsulfones or Z/ E isomeric mixtures. A gram-scale reaction has also been achieved in the presence of a 0.2 mol % catalyst loading.

ChemInform Abstract: Chloride‐Bridged Dinuclear Rhodium(III) Complexes Bearing Chiral Diphosphine Ligands: Catalyst Precursors for Asymmetric Hydrogenation of Simple Olefins.

Efficient rhodium(III) catalysts were developed for asymmetric hydrogenation of simple olefins. A new series of chloride-bridged dinuclear rhodium(III) complexes 1 were synthesized from the rhodium(I) precursor [RhCl(cod)]2 , chiral diphosphine ligands, and hydrochloric acid. Complexes from the series acted as efficient catalysts for asymmetric hydrogenation of (E)-prop-1-ene-1,2-diyldibenzene and its derivatives without any directing groups, in sharp contrast to widely used rhodium(I) catalytic systems that require a directing group for high enantioselectivity. The catalytic system was applied to asymmetric hydrogenation of allylic alcohols, alkenylboranes, and unsaturated cyclic sulfones. Control experiments support the superiority of dinuclear rhodium(III) complexes 1 over typical rhodium(I) catalytic systems.

Chloride-Bridged Dinuclear Rhodium(III) Complexes Bearing Chiral Diphosphine Ligands: Catalyst Precursors for Asymmetric Hydrogenation of Simple Olefins.

Efficient rhodium(III) catalysts were developed for asymmetric hydrogenation of simple olefins. A new series of chloride-bridged dinuclear rhodium(III) complexes 1 were synthesized from the rhodium(I) precursor [RhCl(cod)]2 , chiral diphosphine ligands, and hydrochloric acid. Complexes from the series acted as efficient catalysts for asymmetric hydrogenation of (E)-prop-1-ene-1,2-diyldibenzene and its derivatives without any directing groups, in sharp contrast to widely used rhodium(I) catalytic systems that require a directing group for high enantioselectivity. The catalytic system was applied to asymmetric hydrogenation of allylic alcohols, alkenylboranes, and unsaturated cyclic sulfones. Control experiments support the superiority of dinuclear rhodium(III) complexes 1 over typical rhodium(I) catalytic systems.

Chloride‐Bridged Dinuclear Rhodium(III) Complexes Bearing Chiral Diphosphine Ligands: Catalyst Precursors for Asymmetric Hydrogenation of Simple Olefins

AbstractEfficient rhodium(III) catalysts were developed for asymmetric hydrogenation of simple olefins. A new series of chloride‐bridged dinuclear rhodium(III) complexes 1 were synthesized from the rhodium(I) precursor [RhCl(cod)]2, chiral diphosphine ligands, and hydrochloric acid. Complexes from the series acted as efficient catalysts for asymmetric hydrogenation of (E)‐prop‐1‐ene‐1,2‐diyldibenzene and its derivatives without any directing groups, in sharp contrast to widely used rhodium(I) catalytic systems that require a directing group for high enantioselectivity. The catalytic system was applied to asymmetric hydrogenation of allylic alcohols, alkenylboranes, and unsaturated cyclic sulfones. Control experiments support the superiority of dinuclear rhodium(III) complexes 1 over typical rhodium(I) catalytic systems.

Highly enantioselective hydrogenation of α-oxy functionalized α,β-unsaturated acids catalyzed by a ChenPhos-Rh complex in CF3CH2OH.

Rhodium complexes coordinated by Chenphos are very effective catalysts for the enantioselective hydrogenation of α-aryloxy- and α-alkoxy-substituted α,β-unsaturated carboxylic acids under mild conditions in CF3CH2OH. The catalytic system could be successfully employed in building the core structure of a new FDA approved drug LCZ 696.

Conjugated microporous polymers with chiral BINAP ligand built-in as efficient catalysts for asymmetric hydrogenation

A series of conjugated microporous polymers with chiral BINAP ligand built-in have been synthesized as efficient catalysts for asymmetric hydrogenation.

ChemInform Abstract: Synthesis of Chiral Rh-BICHEP Complexes, Highly Efficient Catalysts for Asymmetric Hydrogenations.

Abstract Chiral cationic and neutral Rh complexes RhX(bichep)(nbd) (XCl,ClO 4 ; nbd=norbornadiene;bichep=2,2′-bis(dicyclohexylphosphino)-6,6′-dimethyl-1,1′-biphenyl) are highly active and excellent catalysts for enantioselective hydrogenation of prochiral olefins and ketones under mild reaction conditions.

Highly effective chiral ortho-substituted BINAPO ligands (o-BINAPO): applications in Ru-catalyzed asymmetric hydrogenations of beta-aryl-substituted beta-(acylamino)acrylates and beta-keto esters.

A novel family of chiral ortho-substituted BINAPO ligands (o-BINAPO) were synthesized from BINOL, and their Ru complexes were highly efficient catalysts for asymmetric hydrogenation of beta-aryl-substituted beta-(acylamino)acrylates and beta-aryl-substituted beta-keto esters. The Ru-bisphosphinite catalysts can tolerate an E/Z mixture of beta-aryl-substituted beta-(acylamino)acrylates. These highly enantioselective hydrogenations provide a useful way to prepare beta-aryl-substituted beta-amino acids and beta-hydroxyl acids.

Efficient Asymmetric Hydrogenation of γ-Amino Ketone Hydrochloride Derivatives Catalyzed by (2S,4S)-4-Dicyclohexylphosphino-2-diphenylphosphinomethyl-1-(N-methylcarbamoyl)-pyrrolidine(MCCPM)-Rhodium complex1

The title complex, (2S,4S)-MCCPM-Rh(I) complex, was found to be an efficient catalyst for asymmetric hydrogenation of γ-amino ketone hydrochloride derivatives.

ChemInform Abstract: General Asymmetric Hydrogenation of Hetero-aromatic Ketones.

trans-RuCl2[(R)-xylbinap][(R)-daipen] or the S,S complex acts as an efficient catalyst for asymmetric hydrogenation of hetero-aromatic ketones. The hydrogenation proceeds with a substrate-to-catalyst molar ratio of 1000−40000 to give chiral alcohols in high ee and high yield. The enantioselectivity appears to be little affected by the properties of the hetero-aromatic ring. This method allows for asymmetric synthesis of duloxetine, an inhibitor of serotonin and norepinephrine uptake carriers.

General asymmetric hydrogenation of hetero-aromatic ketones

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 hydrogenation proceeds with a substrate-to-catalyst molar ratio of 1000-40000 to give chiral alcohols in high ee and high yield. The enantioselectivity appears to be little affected by the properties of the hetero-aromatic ring. This method allows for asymmetric synthesis of duloxetine, an inhibitor of serotonin and norepinephrine uptake carriers.

An Anionic Dinuclear BINAP−Ruthenium(II) Complex: Crystal Structure of [NH2Et2][{RuCl((R)-p-MeO-BINAP)}2(μ-Cl)3] and Its Use in Asymmetric Hydrogenation

Treatment of [RuCl2(COD)]n with (R)-p-MeO-BINAP (p-MeO-BINAP = 2,2‘-bis(bis(p-methoxyphenyl)phosphino)-1,1‘-binaphthyl) in toluene in the presence of triethylamine afforded the anionic dinuclear complex [NH2Et2][{RuCl((R)-p-MeO-BINAP)}2(μ-Cl)3] ((R)-2), whose structure has been determined by an X-ray crystallographic study. Complex 2 is an efficient catalyst for asymmetric hydrogenation of functionalized olefins and ketones.

Efficient Asymmetric Hydrogenation of .ALPHA.-Amino Ketone Derivatives. A Highly Enantioselective Synthesis of Phenylephrine, Levamisole, Carnitine and Propranolol.

The complexes of pyrrolidine bisphosphine ligands (CPMs) with rhodium (I) were found to be efficient catalysts for asymmetric hydrogenation of α-amino ketone hydrochloride derivatives. Utilizing this methodology, we have developed efficient asymmetric syntheses of the optically active β-amino alcohols, phenylephrine, levamisole, carnitine and propranolol.

Efficient Asymmetric Hydrogenation of .BETA.- and .GAMMA.-Amino Ketone Derivatives Leading to Practical Synthesis of Fluoxetine and Eprozinol.

N-(Methylcarbamoyl)-4-(dicyclohexylphosphino)-2-[(diphenylphosphino)methyl]pyrrolidine (MCCPM)- and N-(tert-butoxycarbonyl)-4-(dicyclohexylphosphino)-2-[(diphenylphosphino)methyl]pyrrolidine (BCPM)-rhodium(I) complexes were efficient catalysts for asymmetric hydrogenations of β- and γ-amino ketone hydrochloride derivatives. Utilizing this methodology, we have developed efficient syntheses of fluoxetine and eprozinol from intermediate optically active amino alcohols.

ChemInform Abstract: BICHEP‐Ru Complexes, Highly Efficient Catalysts for Asymmetric Hydrogenation of Carbonyl Compounds.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 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.

BICHEPRu complexes, highly efficient catalysts for asymmetric hydrogenation of carbonyl compounds

Newly prepared [RuX(p-cymene)(bichep)]X, (X = I, Cl) and Ru(OAc) 2(bichep) (bichep = 2,2′-bis(dicyclohexylphosphino)-6,6′-dimethyl-1,1′-biphenyl) proved to be highly efficient catalysts for asymmetric hydrogenation of carbonyl compounds bearing phenylglyoxyloyl group under mild conditions.

Synthesis of chiral Rh-bichep complexes, highly efficient catalysts for asymmetric hydrogenations

Chiral cationic and neutral Rh complexes RhX(bichep)(nbd) (XCl,ClO 4; nbd=norbornadiene;bichep=2,2′-bis(dicyclohexylphosphino)-6,6′-dimethyl-1,1′-biphenyl) are highly active and excellent catalysts for enantioselective hydrogenation of prochiral olefins and ketones under mild reaction conditions.

New chiral ruthenium complexes for asymmetric catalytic hydrogenations

Abstract

『新しい試薬』特集 Ｖ．還元剤 不斉水素化触媒「ＢＩＮＡＰ‐Ｒｕ（ＯＣＯＣＨ３）２錯体」

『新しい試薬』特集 Ｖ．還元剤 不斉水素化触媒「ＢＩＮＡＰ‐Ｒｕ（ＯＣＯＣＨ３）２錯体」

Synthesis of Atropisomeric 2,2′-Bis(dicyclohexylphosphino)-6,6′-dimethyl-1,1′-biphenyl (BICHEP) and Its Use in Rh(I)-catalyzed Asymmetric Hydrogenation of Prochiral Olefins

Abstract The atropisomeric bis(dialkylarylphosphine) ligands, (R)-(−)- and (S)-(+)-2,2′-bis(dicyclohexylphosphino)-6,6′-dimethyl-1,1′-biphenyl (BICHEP) (1) have been newly synthesized, whose Rh(I) complexes are highly efficient catalysts for asymmetric hydrogenations of ethyl α-(benzamido)cinnamate and dimethyl itaconate in up to 98% yields and 98–99% enantiomeric excess.