Highly Efficient Asymmetric Hydrogenation of Activated and Unactivated Ketones Catalyzed by Rhodium(I) Aminophosphine- and Amidophosphine-Phosphinite Complexes. Beneficial Effect of the Non Chiral Ligand

Roucoux, Alain; Devocelle, Marc; Carpentier, Jean‐François; Agbossou, Francine; Mortreux, André

doi:10.1055/s-1995-4959

Cited by 48 publications

(10 citation statements)

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“…Contamination of catalyst surfaces can not be argued as a reason of the induction time observed in this system, because it is well known that clean surfaces are favored when organometallic precursors were used in the preparation of heterogeneous catalysts 29 . a % Conversion at 300 min of reaction.…”

Section: Enantioselective Hydrogenation Reactionsmentioning

confidence: 99%

“…Adding different amounts of a chiral ligand controls the metal average diameters, increasing specific metal surface area, metal dispersion and also obtaining asymmetric heterogeneous catalysts useful in enantioselective hydrogenation of HD, EP, KP and AP, as shown in figure 1. All products of these reactions have applications in chiral drugs syntheses [28][29][30][31][32][33][34][35] .…”

Section: Introductionmentioning

confidence: 99%

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CHIRAL Rh/SiO2 CATALYSTS FOR ENANTIOSELECTIVE HYDROGENATION REACTIONS: THE ROLE OF (S,S)-DIPAMP AS CHIRAL MODIFIER AND STABILIZER ON METALLIC NANOPARTICLES SYNTHESIS

Mella¹,

Ávila²,

SANCHEZ³

et al. 2013

J. Chil. Chem. Soc.

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Rhodium nanoparticles were successfully stabilized by the (S,S)-1,2-ethanediylbis [(2-ethoxyphenyl)phenylphosphine] ((S,S)-DIPAMP) deposited on SiO 2 prepared by a facile reduction and impregnation method. The chiral catalysts obtained were efficient for the enantioselective hydrogenation reactions of prochiral compounds. The catalysts synthesized from [Rh(μ-OMe)(COD)] 2 in the presence of different amounts of a ligand used as chiral stabilizer, showed good metal dispersion. As shown by TEM, the metal particle size ranged between 1 and 2 nm using stabilizer and 9.1 nm was achieved without chiral ligand. Other techniques were used to characterize the chiral catalysts such as X-ray diffraction (XRD), electron diffraction, thermogravimetric analysis (TGA) and N 2 adsorption-desorption isotherms.(S,S)-DIPAMP was used as the stabilizer of metal particles to prevent growing and agglomeration, and it also acts as chiral modifier inducing enantioselectivity in the asymmetric hydrogenation of 3,4-hexanodione (HD), ethyl pyruvate (EP), ketopantolactone (KP), and acetophenone (AP). Under specific conditions such as 25 °C, 40 bar of H 2 and substrate/Rh=100, 1%Rh-(S,S)-DIPAMP/SiO 2 chiral catalysts showed excellent catalytic performance with conversion and enantiomeric excess (ee) levels up to 99% and 54% respectively.

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Section: Enantioselective Hydrogenation Reactionsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

CHIRAL Rh/SiO2 CATALYSTS FOR ENANTIOSELECTIVE HYDROGENATION REACTIONS: THE ROLE OF (S,S)-DIPAMP AS CHIRAL MODIFIER AND STABILIZER ON METALLIC NANOPARTICLES SYNTHESIS

Mella¹,

Ávila²,

SANCHEZ³

et al. 2013

J. Chil. Chem. Soc.

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“…Several chirally modified Rh and Ru catalysts have been applied in this reaction. Hydrogenation of 2-aminoacetophenone hydrochloride catalyzed by MOC-BIMOP-[Rh(nbd) 2 ]ClO 4 [118] or [RhX(cy,cy-oxopronop)] 2 (X = Cl, OCOCF 3 ) [119] provides the corresponding amino alcohol in 93% ee (Fig. 32.36).…”

Section: Hetero-substituted Aromatic Ketonesmentioning

confidence: 99%

Enantioselective Ketone and β‐Keto Ester Hydrogenations (Including Mechanisms)

Ohkuma¹,

Noyori²

2006

The Handbook of Homogeneous Hydrogenation

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Enantioselective hydrogenation of b-keto esters is a well-established procedure to produce chiral b-hydroxy esters in high optical purity [1][2][3][4]. Many important biologically active compounds have been synthesized through this procedure, even on a commercial scale [1][2][3][4]. Ru complexes [5] bearing appropriate chiral phosphine ligands [6][7][8] provide excellent catalytic efficiency for this reaction. Certain chiral Rh catalysts [3,4] and heterogeneous Ni catalysts [9] are also utilized. The recent development of the chiral diphosphine/diamine-Ru catalyst enables rapid and stereoselective hydrogenation of simple ketones without a hetero-atom functionality close to the carbonyl group [2,4]. These enantioselective transformations are summarized in the present chapter. Chiral LigandsIn enantioselective hydrogenation of ketonic substrates, the excellent catalytic performance such as high turnover number (TON), turnover frequency (TOF = -TON h -1 or s -1 ), and enantioselectivity is achievable only when (pre)catalysts are prepared by the appropriate combination of metal species and chiral ligands [6-8, 10, 11]. Stereo-repulsive interaction between substituents of ligands and substrates is normally utilized for the regulation of stereochemistry. The metal and ligand must be carefully selected because of the diversity of substrate structures [1][2][3][4][5]. Chiral diphosphine ligands with a C 2 symmetry (see Fig. 32.1) have played a main role in this respect. Recently, however, various effective C 1 phosphine ligands as well as phosphinite ligands have been developed, the structures of which are illustrated in Figures 32.2 and 32.3, respectively. Chiral amine and imine ligands (Fig. 32.4) are also useful, particularly when they are coupled with a chiral diphosphine ligand in the hydrogenation of simple ketones [2,4,5]. Immobilized BINAPs are detailed in Figure 32.5.

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“…The reaction has been extensively studied using chiral Rh, Ru, Cr, and Ir complexes that afford at best close to 99% ee [26][27][28][29][30][31]. Chiral heterogeneous catalysts are less efficient so far.…”

Section: Introductionmentioning

confidence: 99%