Hydrogenation of olefins by iridium metal complexes of amine and ether substituted phosphines by James Lee Clements

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  • Alkenes.

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Statementby James Lee Clements.
The Physical Object
Paginationix, 39 l. :
Number of Pages39
ID Numbers
Open LibraryOL16727009M

Download Hydrogenation of olefins by iridium metal complexes of amine and ether substituted phosphines

Asymmetric hydrogenation is one of the most important catalytic methods for the preparation of optically active compounds.

For a long time the range of olefins that could be hydrogenated with high enantiomeric excess was limited to substrates bearing a coordinating group next to the CC bond. We have found a new class of catalysts, iridium complexes with chiral P, N ligands, that overcome these Cited by:   Compared to their rhodium- and ruthenium-based cohorts, iridium catalysts are new to the asymmetric hydrogenation of olefins.

Using an achiral catalyst, Crabtree and co-workers established the ability of iridium compounds to rapidly hydrogenate olefins.Crabtree's catalyst, [(COD)Ir(PCy 3)(py)] + [PF 6] − (1, Scheme 2, COD = 1,5-cyclooctadiene, py = pyridine), catalyzes the hydrogenation Cited by: Butene hydrogenation catalyzed by iridium-alumina has been studied over the range 20–°C.

Isomerization of butene to butene accompanied hydrogenation, and the kinetics of both processes are reported. The formation of chemisorbed butyl groups was rate-determining both in hydrogenation and in isomerizationCited by: 8.

dihydrido olefin complexes. Such complexes had been assumed (I, 13) to be intermediates in the hydrogenation of olefins but never directly observed.

They may be formed either, as above, by hydrogen addition to an olefin complex or by olefin addition to a hydride complex (I I):. Chiral iridium complexes with bicyclic pyridine-based N,P ligands have emerged as efficient catalysts for the enantioselective hydrogenation of unfunctionalized trialkyl-substituted olefins.

This chapter focuses on the hydrogenation reactions catalyzed by transition metal complexes, with the aim of developing catalysts for selective hydrogenation under mild conditions. Olefin hydrogenations—for example—are important industrial processes, and selectivity is critical to the success of such processes.

Iridium complexes derived from chiral P,N ligands are efficient catalysts for the enantioselective hydrogenation of 2‐aryl‐substituted terminal alkenes. Using –1 mol % of catalyst at room temperat.

Comparison of cationic rhodium and iridium complexes in directed homogeneous hydrogenation. Tetrahedron41 (20), DOI: /S(01) John M. Brown, Andrew E. Derome, Stephen A. Hall. Nature of the catalytic cycle in iridium-complex catalysed hydrogenation of unsaturated alcohols.

Metal complexes of functionalized phosphines-I. Synthesis and characterization of 2-diphenylphosphinoethylamines and some of their complexes with platinum.

X-ray structure of [HBut)(Ph2PCH2CH2NHButHCl)Cl]ClH2O. Polyhedron10 (), DOI: /S(00)X. Iridium‐catalyzed asymmetric hydrogenation of prochiral halogenated ketones was successfully developed to prepare various chiral halohydrins with high reactivities and excellent enantioselectivities under basic reaction condition (up to >99% conversion, 99% yield, >99% ee).

Imine Hydrogenation by Tribenzylphosphine Rhodium and Iridium Complexes. Organometallics25 (2), DOI: /om Alceo Macchioni. Ion Pairing in Transition-Metal Organometallic Chemistry. Chemical Reviews(6), DOI: /cr Iridium catalysts have been prepared with bi- and tri-dentate ligands, which resemble the cobalt catalysts shown in Section A SABRE catalyst, which utilises a bidentate carbene ligand, has been synthesised by Ruddlesden et al.

and the solvent capability of SABRE investigated [41].In d 2-DCM, an enhancement of fold was observed for the ortho-proton resonances. N-heterocyclic carbene–phosphine complexes of iridium have been synthesized and examined for their performance in the catalytic homogeneous hydrogenation of a range of olefins; the reaction was.

The Effect of Halo Ligand on the Rate of Hydrogenation of Coordinated Olefin in Dihydrido-olefin Complexes RhXH 2 (ol) (PPh 3) 2 (X=Cl, Br, I).

Bulletin of the Chemical Society of Japan52 (12). Download Citation | Ligands for Iridium-catalyzed Asymmetric Hydrogenation of Challenging Substrates: Reactivity and Catalysis | Cationic iridium complexes based on.

The earliest examples of this reaction were carried out mainly on perfluorinated compounds, with differing levels of success [].For example, in the late s Knunyants et al. reported the successful hydrogenation of perfluoropropene 1 under standard conditions—a heterogeneous palladium catalyst at room temperature—to give the desired 1,1,1,2,3,3-hexafluoropropane 2 in a 96%.

were prepared and screened in the iridium catalysed hydrogenation reaction using a series of previously developed N,P-ligated Ir-catalysts.

The outcome lylic Alcohols with an Iridium–N,P Complex. Li, B. Peters, and Iridium-catalysed asymmetric hydrogenation of olefins using TIQ phosphine-oxazoline ligands.

Chakka, B. Jiang et al. have reported on the use of a small family of chiral SPOs for the asymmetric hydrogenation of imines (see Chapter ).

As shown in Sch an iridium complex of (R)-phenyl-t-butyl SPO furnished the (S)-amine 86 in 80% ee and more than 99% yield after 24 h of hydrogenation at 25 bars. Although this enantioselectivity may.

High turnover numbers and up to 98% ee were obtained in the catalytic hydrogenation of unfunctionalized aryl-substituted olefins with iridium–phosphanyldihydrooxazole complexes 1.

The catalytic hydrogenation of olefins proceeds through protonation and subsequent hydride attack. Electron‐deficient phosphines and diarlyamines were demonstrated to be viable Lewis bases for the reaction, thus allowing catalyst loadings of 10 to 5 mol %.

Asymmetric hydrogenation is a chemical reaction that adds two atoms of hydrogen preferentially to one of two faces of an unsaturated substrate molecule, such as an alkene or ketone. The selectivity derives from the manner that the substrate binds to the chiral jargon, this binding transmits spatial information (what chemists refer to as chirality) from the catalyst to the target.

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Hydrogenation of amides to amines is an important reaction, but the need for high temperatures and H 2 pressures is a problem. Catalysts that are effective under mild reaction conditions, that is, lower than 30 bar H 2 and 70 °C, have not yet been reported.

Here, the mild hydrogenation of amides was achieved for the first time by using a Pt‐V bimetallic catalyst. Keywords: Hydrogenation, iridium catalyst, chiral pool, pyridine-phosphinite, asymmetric Introduction Cationic iridium complexes with chiral P,N ligands have proved to be efficient catalysts for the hydrogenation of a wide range of functionalized and unfunctionalized olefins,1 Unlike Rh- and.

In the early-transition metals titanium and zirconium complexes are frequently used. Dimethyl titanocene [CpTi(CH 3) 2] was found to be widely applicable to primary aryl or alkyl amines and substituted alkynes.

Titanium-imido complex is a catalytically active species which allows [2 + 2] cycloaddition of alkynes [7]. A series of diphosphines of the novel Walphos ligand family all based on a phenylferrocenylethyl backbone were synthesised in a four‐step sequence.

In the rhodium‐ or ruthenium‐catalysed asymmetric hydrogenation of olefins and ketones enantioselectivities of. Ranging from hydrogenation to hydroamination, cycloadditions and nanoparticles, this first handbook to comprehensively cover the topic of iridium in synthesis discusses the important advances in iridium-catalyzed reactions, namely the use of iridium complexes in enantioselective catalysis.

A must for organic, complex and catalytic chemists, as well as those working with/on organometallics. Abstract Asymmetric hydrogenation is one of the most important catalytic methods for the preparation of optically active compounds. For a long time the range of olefins that could be hydrogenated with high enantiomeric excess was limited to substrates bearing a coordinating group next to the C+C bond.

A set of iridium(I) and iridium(III) complexes is reported with triazolylidene ligands that contain pendant benzoxazole, thiazole, and methyl ether groups as potentially chelating donor sites. The bonding mode of these groups was identified by NMR spectroscopy and X-ray structure analysis. The complexes were evaluated as catalyst precursors in transfer hydrogenation and in acceptorless alcohol.

In chemistry, an alkene is a hydrocarbon that contains a carbon–carbon double bond. The term is often used as synonym of olefin, that is, any hydrocarbon containing one or more double bonds. However, the IUPAC recommends using the name "alkene" only for acyclic hydrocarbons with just one double bond; alkadiene, alkatriene, etc., or polyene for acyclic hydrocarbons with two or more double.

The selective synthesis of linear amines from internal olefins or olefin mixtures was achieved through a catalytic one-pot reaction consisting of an initial olefin isomerization followed by hydroformylation and reductive amination.

Key to the success is the use of specially designed phosphine ligands in the presence of rhodium catalysts. This reaction constitutes an economically attractive and. mechanism of homogeneous hydrogenation by anionic ruthenium hydride complexes. The activity of the orthometallated species K+[RuH 2(PPh 3) 2(PPh 26 6H 4)]- in homogeneous hydrogenation was reported in when it was shown to reduce ketones, esters, nitriles and polycyclic aromatics as well as olefins.

The invention relates to a process for the selective partial hydrogenation of conjugated diene compounds comprising at least one, preferably terminal, diene function and at least one additional carbon-carbon double bond, said process comprising reacting the conjugated diene compounds with hydrogen in the presence of a nickel-NHC based catalyst.

Precious transition metals, such as rhodium, iridium, and ruthenium, play a crucial role in homogeneous catalysis of asymmetric hydrogenation. 1 However, they are expensive rare metals and are anticipated to be limited by the depletion of natural resources in the future. Hence, the investigation and development of sustainable methods using abundant and cheap base transition metals is.

Iridium is generally considered to be a less effective catalyst than the other platinum metals but when highly co-ordinatively unsaturated species of it are prepared they appear to be exceptionally active hydrogenation catalysts, even for reduction of sterically hindered olefins.

A mechanism for this reaction has been postulated based on low temperature magnetic resonance evidence. Transition metal complexes of a novel tetradentate phosphine and of a new diphosphine ether Mark R. Mason hydrogénation, olefin isomerization, olefin oligomerization and olefin hydrocyanation (a The less basic phenyl substituted phosphines CH3C(CH2PPh2)3 and PhP(Œ2CH2PPh2)2, as well as the non-chelating but highly.

Among the known group VIII transition metal complexes, the most effective catalyst for hydrogenation of simple aromatic ketones is the Ru-BINAP-chiral diamine-KOH system disclosed, for example, in X. Zhang, et al. Chem.

Soc.,which produced an enantiomeric excess on the order of %. Seung Wook Kim, Leyah A. Schwartz, Jason R. Zbieg, Craig E. Stivala, Michael J. Krische, Regio- and Enantioselective Iridium-Catalyzed Amination of Racemic Branched Alkyl-Substituted Allylic Acetates with Primary and Secondary Aromatic and Heteroaromatic Amines, Journal of the American Chemical Society, /jacs.8b, ().

Abstract. In this chapter the application of transition metal nitrosyl complexes in homogeneous catalysis has been reviewed. Particular attention was paid to the function of nitrosyl as: (1) a π-accepting ancillary ligand; (2) a non-innocent ligand capable of reversible linear/bent transformations triggering catalytic reaction courses; (3) a redox-active ligand functioning as a “nitrosyl.

Selective hydrogenation of olefins is an important process in both chemical and pharmaceutical industries. This chapter reviews intriguing catalytic studies accomplished by employing a variety of catalysts such as metal complexes, supported materials, supported metal complexes, and nanosized materials for polyene hydrogenation.

In addition, new research area involving unsupported colloidal. complexes, with phosphines, hydrogenation using, a: 38 dealkylation of xylenes with H 2 O on, a: hydrogenations of C 6 H 6, C 6 H 5 NO 2 on, a: polymer-supported, olefin reduction using, a: 36 Rhodium Acetate, hydrogenation of olefins with, a: Rhodium Boride, H 2 adsorption on, a:   Complexes of cobalt and nickel with tridentate ligand PNHPR are effective for hydrogenation of unsaturated compounds.

Cobalt complex [(PNHPCy)Co(CH2SiMe3)]BArF4 (PNHPCy=bis[2-(dicyclohexylphosphino)ethyl]amine, BArF4=B(3,5-(CF3)2C6H3)4)) was prepared and used with hydrogen for hydrogenation of alkenes, aldehydes, ketones, and imines under mild .Unfortunately, the iridium complex Ir prepared from this ligand proved to be an inefficient catalyst.

The enantioselectivities in the hydrogenation of various test substrates were much lower than those induced by the tert-butyloxazoline analog with the exception of .

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