Rhodium(I) and platinum(II) complexes of aminomethylphosphines as hydrogenation and hydroformylation catalysts

Hoye, Peter A. T.; Kemmitt, R. D. W.; Law, Dave

doi:10.1002/aoc.590070710

Cited by 17 publications

(3 citation statements)

References 9 publications

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“…Preparation of (R)-4: (2R,5R)-1-Hydroxy-1-oxo-2,5-diphenylphospholane (2.33 g, 8.56 mmol) was suspended in toluene (15 mL) before phenylsilane (1.435 g, 1.635 mL, 13.26 mmol) was added dropwise by syringe. The (12), RhÀP(2) 2.3101 (10), RhÀP(3) 2.3002 (10), RhÀHA 1.52 (2), RhÀHB 1.53 (2), RhÀHC 1.52 (2); P(1)-Rh-P(2) 89.98(4), P(1)-Rh-P(3) 90.93(3), P(2)-Rh-P(3) 90.83(4), P(1)-Rh-HA 91.3 (16), P(2)-Rh-HA 96.5 (16), P(3)-Rh-HA 172.3 (16), P(1)-Rh-HB 177.0 (14), P(2)-Rh-HB 90.7 (14), P(3)-Rh-HB 92.0 (14), P(1)-Rh-HC 90.4(13), P(2)-Rh-HC 178.4(12), P(3)-Rh-HC 90.7 (12), HA-Rh-HB 86 (2), HA-Rh-HC 82 (2), HB-Rh-HC 88.8 (19).…”

Section: Methodsmentioning

confidence: 99%

“…Additional stirring for 1 h at 10 8C afforded a white powder that was filtered and washed with cold THF (2 2 mL) to afford 3 (1.1 g, 5.1 mmol, 49 %). 1 H NMR (600.13 MHz, MeOD, 295 (2), HB-Rh-HC 88.8 (19).…”

Section: P{mentioning

confidence: 99%

“…Keywords: asymmetric catalysis · hydrogenation · ligand design · phospholanes · rhodium satility, only limited attempts to synthesise the corresponding chiral amine-bridged di-and triphosphanes have been made. Initially, mainly chiral amines and amino acids were used, [7,19] and only recently have there been several reports dealing with the introduction of chiral phosphorus building blocks. [20] We have therefore focused on the development of a modular synthesis of a large family of bi-and tridentate chiral phospholane ligands and selected the 2,5-dimethyl-and 2,5diphenyl-substituted phospholanes as stereodirecting groups because these two privileged chiral units had given rise to remarkable reactivity and enantioselectivities with particular impact on catalytic asymmetric hydrogenations.…”

Section: Introductionmentioning

confidence: 99%

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Stitching Phospholanes Together Piece by Piece: New Modular Di‐ and Tridentate Stereodirecting Ligands

Lloret‐Fillol¹,

Kruckenberg²,

Scherl³

et al. 2011

Chemistry A European J

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The modular one-pot synthesis of a large family of bi- and tridentate 2,5-dimethyl- and 2,5-diphenyl-substituted phospholanes employs air-stable chiral phospholanium chloride salts and primary amines or NH(4)Cl as starting materials. These were transformed into the C(2)-symmetric dimethyl- and diphenylphospholane ligands, which reacted with [Rh(cod)(2)]BF(4) (cod=1,5-cyclooctadiene) to yield the rhodium complexes [Rh(L)(cod)]BF(4) (L=bisphospholane ligands). The corresponding trisphospholane complexes, 11 and 12, were obtained in high yields (81 and 92%, respectively), and fully characterised by NMR spectroscopy, mass spectrometry and elemental analysis. Whilst in the C(3)-symmetric complex 11, containing the tridentate 2,5-dimethylphospholane, the ligand is bound symmetrically, different coordination behaviour was found for the diphenyl-substituted complex 12, in which the coordination of only two of the three phospholane moieties to the metal centre was observed. A DFT study at the B3PW91 level established minimum energy structures consistent with experimental findings in solution and in the solid state. The non-coordinated phospholane unit present in 12 allowed further modification of the complex through the coordination of Au(I)-X (X=Cl, C(6)F(5) and tris(trifluoromethyl)phenyl ((F)Mes)) fragments to the pendant phosphane. To investigate the potential of the new ligands, the enantioselective hydrogenation of a series of prochiral olefins as benchmark substrates, using isolated Rh complexes as catalysts, was studied. The substrates included methyl esters of three dehydro-α-acetamido acids and two itaconic acid derivatives. In general good to excellent enantioselectivities (of up to >99% ee) were observed. Ligand backbone modification by coordination of bulky Au-X substituents to the free phospholane unit in complex 12 led to an outstanding enhancement of the catalyst performance and there was a clear correlation between the properties of the complex periphery and the enantioselectivity.

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Section: Methodsmentioning

confidence: 99%

Section: P{mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Stitching Phospholanes Together Piece by Piece: New Modular Di‐ and Tridentate Stereodirecting Ligands

Lloret‐Fillol¹,

Kruckenberg²,

Scherl³

et al. 2011

Chemistry A European J

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Chiral Catalysts

Kégl

Kollár

2002

Encyclopedia of Catalysis

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The application of optically active compounds is steadily increasing due to their biological importance. The most efficient way for their synthesis is catalysis, i.e., a reaction where a small amount of chiral material (catalyst) can transmit chirality to a large amount of substrate. Of the various types of chiral catalysts, the present article is dealing exclusively with those containing transition metals in liquid phase. In the first part of the article the chiral ligands are arranged according to their donor atoms, and classified as phosphanes (mono‐ and bidentate phosphanes possessing various elements of chirality), nitrogen, and oxygen ligands, etc. This section is followed by chiral catalysts grouped systematically according to their central metal. (The discussion is restricted to those homogeneous chiral catalysts, where the chemical transformation of an achiral substrate possessing enantiotopic groups, atoms, faces, or centers into one enantiomer takes place.) While in the “ligand section,” the seminal works on the synthesis of the most widely used basic ligands and their first applications are demonstrated, in the “metal section,” the most recent applications (over the past 5 years) are discussed.

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Chiral Catalysts

Kégl

Kollár

2010

Encyclopedia of Catalysis

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The application of optically active compounds is steadily increasing due to their biological importance. The most efficient way for their synthesis is catalysis, that is a reaction where a small amount of chiral material (catalyst) can transmit chirality to a large amount of substrate. Of the various types of chiral catalysts, the present article deals exclusively with those containing transition metals in the liquid phase. In the first part of the article, the chiral ligands are arranged according to their donor atoms and are classified as phosphanes (mono‐ and bidentate phosphanes, possessing various elements of chirality), nitrogen and oxygen ligands, chiral dienes, etc. This section is followed by chiral catalysts grouped systematically according to their central metal. (The discussion is restricted to those homogeneous chiral catalysts, where the chemical transformation of an achiral substrate possessing enantiotopic groups, atoms, faces, or centers into one enantiomer takes place.) While the section dealing with ligand, the seminal works on the synthesis of the most widely used basic ligands and their first applications are also demonstrated and in the section dealing with metal mainly the recent catalytic (synthetic) applications over the past 10 years are discussed.

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Rhodium(I) and platinum(II) complexes of aminomethylphosphines as hydrogenation and hydroformylation catalysts

Cited by 17 publications

References 9 publications

Stitching Phospholanes Together Piece by Piece: New Modular Di‐ and Tridentate Stereodirecting Ligands

Stitching Phospholanes Together Piece by Piece: New Modular Di‐ and Tridentate Stereodirecting Ligands

Chiral Catalysts

Chiral Catalysts

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