Asymmetric Hydrogenation Of Itaconic Acid Research Articles

Unusual deactivation in the asymmetric hydrogenation of itaconic acid

The formation of unusual Rh(III) substrate complexes from [Rh(DIPAMP)(MeOH) 2]BF 4 and itaconic acid has been detected which leads to the deactivation of the catalyst. The influence of different parameters on the formation of such complexes, namely substrate concentration, reaction time, temperature, acidic and basic additives, was investigated with different NMR methods. Two different Rh(III) substrate complexes are formed whose ratio is strongly dependent on substrate concentration and reaction time. The pH value of the solution shows a strong influence on the chemical shifts of the 31P NMR signals of such complexes. A catalyst-mediated esterification of itaconic acid in methanol was detected. Extended investigations provide detailed 1H, 13C and 31P NMR data for the Rh(III) complexes and information about their stability in solution.

ChemInform Abstract: Asymmetric Hydrogenation of Prochiral Carboxylic Acids Catalyzed by the Five-Coordinate Ruthenium(II)-Hydride Complex (RuH(binap)2)PF6 ( binap: (R)- or (S)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl).

Abstract The five-coordinate complex [RuH(binap)2]PF6 (I, binap = (R)- or (S)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl) has been found to have sufficient catalytic activity for asymmetric hydrogenation of itaconic acid and other prochiral carboxylic acids under mild conditions. The catalytic hydrogenation of itaconic acid by I was examined under a variety of conditions, and the addition of triethylamine was found to effect high enantioselectivities (> 90% ee). 1H and 31P NMR examinations of reaction mixtures of I and itaconic acid under conditions similar to the hydrogenation suggested the formation of ruthenium species containing one binap chelate.

Unusual Deactivation in the Asymmetric Hydrogenation of Itaconic Acid

Abstractmagnified imageDuring the asymmetric hydrogenation of itaconic acid with rhodium solvate complexes of the type [Rh(PP)(MeOH)2] BF4 (PP=DIPAMP, Me‐DuPHOS) a deactivation with increasing substrate concentration is observed. It is shown that this inhibition phenomenon is due to the in situ formation of an inactive rhodium(III)‐alkyl complex. Two crystal structures of single crystals of the responsible complexes (1) and (2) support the deactivation pathway.

Enantioselective hydrogenation of olefins by chiral iridium phosphorothioite complex covalently anchored on mesoporous silica

Chiral monodentate phosphorous-based ligands have proven effective for the enantioselective hydrogenation of olefins. Binol-derived monodentate phosphorothioite (PS) ligand was synthesized from binol and thiopropyltriethoxysilane, and its iridium complex was covalently anchored to mesoporous silica supports like SBA-15, MCM-41, and MCM-48. These catalysts were characterized by different physicochemical techniques and assessed for their catalytic performances in the heterogeneous asymmetric hydrogenation of itaconic acid and its derivatives. It was found that the catalytic activities and enantioselectivities of the heterogenized iridium complex (IrPSSBA-15) in the hydrogenation reactions were comparable to its homogeneous analogue. Binol-derived monodentate phosphorothioite ligand in heterogeneously anchored form (iridium complex) is a more effective catalyst than the reported monodentate phosphorous ligand systems in the hydrogenation reactions, possibly due to the changes in electronic properties around the iridium metal center. The effects of substrate-to-catalyst molar ratio, solvents, and temperature on substrate conversions and enantioselectivities of the products were investigated in hydrogenation reactions.

Asymmetric Hydrogenation of Itaconic Acid and Enol Acetate Derivatives with the Rh‐TangPhos Catalyst.

The Rh-TangPhos catalyst has been used for asymmetric hydrogenation of itaconic acid and enol acetate derivatives. A variety of chiral 2-substituted succinic acids and chiral acetates have been obtained in excellent ee values (up to 99% ee).

Asymmetric hydrogenation of itaconic acid and enol acetate derivatives with the Rh-TangPhos catalyst.

[reaction: see text] The Rh-TangPhos catalyst has been used for asymmetric hydrogenation of itaconic acid and enol acetate derivatives. A variety of chiral 2-substituted succinic acids and chiral acetates have been obtained in excellent ee values (up to 99% ee).

Chiral Mono- and Bidentate Ligands Derived from D-Mannitol and Their Application in Rhodium(I)-Catalyzed Asymmetric Hydrogenation Reactions

The new monodentate phosphoramidites 8a−g and bidentate phospholanes 13a−e are prepared in an ex-chiral-pool synthesis from D-mannitol. Chiral diols 7a−g, obtained via nucleophilic ring opening of bis(epoxides) 6a−b, are the key intermediates for the production of both classes of ligands. Treatment of 8a−g or 13a−e with [PdCl2(COD)] or [Rh(COD)2][SO3CF3] yield the corresponding Pd (10a, 10f, 15a) and Rh compounds (9a−g and 14a−e), respectively. The C2 symmetry of the complexes in the solid state is demonstrated by X-ray structure investigations performed on 10a, 10f and 15a. Surprisingly high enantioselectivities in the asymmetric hydrogenation of itaconic acid (94% ee) and α-acetamidocinnamic acid (89% ee) are observed on using the Rh complex 9g bearing two monodentate phosphoramidite ligands. Although the chelating bis(phospholanes) described herein are more effective, the adjustable synthesis of the monodentate phosphoramidites may permit the optimization of asymmetric catalytic reactions. (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

Catalytic hydrogenation of itaconic acid in a biotinylated Pyrphos–rhodium(I) system in a protein cavity

The construction of a chiral catalyst system embedded at a specific site in a protein has been studied. The preparation of the biotinylated Pyrphos–Rh(I) complex attached to the binding site in avidin and its application to the asymmetric hydrogenation of itaconic acid have been investigated. By introducing the chiral Pyrphos–Rh(I) moiety into the constrained environment of the protein cavity it was found that the enantioselectivity of the system was significantly influenced by the tertiary conformation within the avidin cavity. The effects of reaction conditions such as temperature, hydrogen pressure, and the pH value of the buffer on enantioselectivity are reported.

Asymmetric hydrogenation of prochiral carboxylic acids catalyzed by the five-coordinate ruthenium(II)-hydride complex [RuH(binap) 2]PF 6(binap = R- or S-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl)

The five-coordinate complex [RuH(binap)2]PF 6 (I, binap = ( R)- or ( S)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl) has been found to have sufficient catalytic activity for asymmetric hydrogenation of itaconic acid and other prochiral carboxylic acids under mild conditions. The catalytic hydrogenation of itaconic acid by I was examined under a variety of conditions, and the addition of triethylamine was found to effect high enantioselectivities (> 90% ee). 1H and 31P NMR examinations of reaction mixtures of I and itaconic acid under conditions similar to the hydrogenation suggested the formation of ruthenium species containing one binap chelate.

ChemInform Abstract: Asymmetric Reactions Catalyzed by Chiral Metal Complexes. Part 34. The Effects of cis‐Coordinating Phosphine of Chiral Bisphosphine (IV). Rhodium Complexes on the Catalytic Activities in the Asymmetric Hydrogenation of Itaconic Acid (V).

ChemInformVolume 20, Issue 48 Preparative Organic Chemistry ChemInform Abstract: Asymmetric Reactions Catalyzed by Chiral Metal Complexes. Part 34. The Effects of cis-Coordinating Phosphine of Chiral Bisphosphine (IV). Rhodium Complexes on the Catalytic Activities in the Asymmetric Hydrogenation of Itaconic Acid (V). H. TAKAHASHI, H. TAKAHASHI Sch. Pharm. Sci., Univ. Shizuoka, Yada, Shizuoka 422, JapanSearch for more papers by this authorN. YAMAMOTO, N. YAMAMOTO Sch. Pharm. Sci., Univ. Shizuoka, Yada, Shizuoka 422, JapanSearch for more papers by this authorH. TAKEDA, H. TAKEDA Sch. Pharm. Sci., Univ. Shizuoka, Yada, Shizuoka 422, JapanSearch for more papers by this authorK. ACHIWA, K. ACHIWA Sch. Pharm. Sci., Univ. Shizuoka, Yada, Shizuoka 422, JapanSearch for more papers by this author H. TAKAHASHI, H. TAKAHASHI Sch. Pharm. Sci., Univ. Shizuoka, Yada, Shizuoka 422, JapanSearch for more papers by this authorN. YAMAMOTO, N. YAMAMOTO Sch. Pharm. Sci., Univ. Shizuoka, Yada, Shizuoka 422, JapanSearch for more papers by this authorH. TAKEDA, H. TAKEDA Sch. Pharm. Sci., Univ. Shizuoka, Yada, Shizuoka 422, JapanSearch for more papers by this authorK. ACHIWA, K. ACHIWA Sch. Pharm. Sci., Univ. Shizuoka, Yada, Shizuoka 422, JapanSearch for more papers by this author First published: November 28, 1989 https://doi.org/10.1002/chin.198948082AboutPDF 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. Volume20, Issue48November 28, 1989 RelatedInformation

ChemInform Abstract: Highly Efficient Asymmetric Hydrogenation of Itaconic Acid Derivatives Catalyzed by a Modified DIOP‐Rhodium Complex.

Abstract A modified DIOP analogue bearing 4-methoxy and 3,5-dimethyl groups on each phenyl group has been synthesized. The rhodium complex of the ligand has been found to give very high optical yields in the asymmetric hydrogenation of itaconic acid and its derivatives bearing β-aryl groups, the products of which are the key-intermediates for optically active lignan derivatives.

The Effects of cis-Coordinating Phosphine of Chiral Bisphosphine–Rhodium Complexes on the Catalytic Activities in the Asymmetric Hydrogenation of Itaconic Acid

Abstract The effects of cis-coordinating phosphine of the rhodium complexes of BCPM ((2S,4S)-N-(t-butoxycarbonyl)-4-(dicyclohexylphosphino)-2-[(diphenylphosphino)methyl]pyrrolidine) analogues bearing electron donating or attracting groups on the catalytic activities in the asymmetric hydrogenation of itaconic acid are described.

Highly efficient asymmetric hydrogenation of itaconic acid derivatives catalyzed by a modified DIOP-rhodium complex

A modified DIOP analogue bearing 4-methoxy and 3,5-dimethyl groups on each phenyl group has been synthesized. The rhodium complex of the ligand has been found to give very high optical yields in the asymmetric hydrogenation of itaconic acid and its derivatives bearing β-aryl groups, the products of which are the key-intermediates for optically active lignan derivatives.

Dramatic Hydrogen Pressure and Triethylamine Effects on the Asymmetric Hydrogenation of Itaconic Acid Which Give a New Mechanistic Aspect on Asymmetric Induction

Abstract Dramatic hydrogen pressure and triethylamine effects on the asymmetric hydrogenation of itaconic acid catalyzed by BCPM-Rh+ and an explanation for these effects were described.

PENTOSE AMIDOPHOSPHITES. SYNTHESIS, PALLADIUM COMPLEXES

Abstract Glycoamidophosphites in the pentose series have been synthesized based on 2,3-O-isopropylidene-β-methyl-D-ribofuranoside, 1,2-O-isopropylidene-α-D-xylofuranose, xylitane and 3,5-O-isopropylidenexylitane. Some of these compounds are used as ligands for the synthesis of the palladium complexes. Consideration is given to the behavior of these complexes as catalysts in the asymmetric hydrogenation of itaconic acid.

HIGHLY EFFECTIVE CATALYTIC ASYMMETRIC HYDROGENATION OF ITACONIC ACID WITH NEW CATIONIC CHIRAL PYRROLIDINEPHOSPHINE–RHODIUM COMPLEXES

Abstract Syntheses of new cationic chiral pyrrolidinephosphine–rhodium complexes and their application to the asymmetric hydrogenation of itaconic acid were described. Thus, PPPM-, BZPPM-, FPPM- and BPPM-Rh+ in the presence of triethylamine gave S-(−)-methylsuccinic acid in 87.1, 88.9, 94.2 and 93.6% optical yields respectively.

PREPARATION OF CHIRAL AMINOPHOSPHINE LIGANDS AND THEIR USE IN ASYMMETRIC HOMOGENEOUS HYDROGENATION OF ITACONIC ACID

Abstract Optically active aminophosphines were prepared via ortho-directed metalation of appropriate arylamines followed by introduction of a diphenylphosphino group. These aminophosphines were used as ligands in the rhodium complex-catalyzed asymmetric hydrogenation of itaconic acid. Although moderate optical yields (up to 43% ee) were obtained, the stereochemical outcome with each ligand depended markedly on the chelate effect of the aminophosphines which played a significant role in both catalytic activity and enantioselectivity.

Highly enantioselective catalytic asymmetric hydrogenation of itaconic acid

Highly enantioselective catalytic asymmetric hydrogenation of itaconic acid