Catalyst Inhibition and Deactivation in Homogeneous Hydrogenation

Heller, Detlef; Vries, André H.M. de; Vries, Johannes G. de

doi:10.1002/9783527619382.ch44

Cited by 32 publications

(41 citation statements)

References 108 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The ratio of the rate constants for the hydrogenation of the diolefine complexes is approximately 5.3 [3]. It is well known that the double bonds of the diolefines are not coordinated perpendicular to the PRhP plane.…”

Section: Discussionmentioning

confidence: 96%

Crystal structure of (η4-cycloocta-1,5-dien)-N-(2-(diphenylphosphinooxy)- 3-(naphthalen-1-yloxy)propyl)-N-(pentan-3-yl)-1,1-diphenylphosphinamine- rhodium(I) tetrafluoroborate, [Rh(C8H12)(C42H43NO2P2)][BF4]

Dai¹,

Heller²,

Preetz³

et al. 2007

Zeitschrift Für Kristallographie - New Crystal Structures

Self Cite

View full text Add to dashboard Cite

Source of materialThe synthesis is described in [1]. DiscussionUnexpected differences between the title compound and the related norborna-2,5-diene complex in the catalytic hydrogenation of the diolefines norborna-2,5-diene and (Z,Z)-cycloocta-1,5-diene [2] motivated us to determine the crystal structure of the title compound. The ratio of the rate constants for the hydrogenation of the diolefine complexes is approximately 5.3 [3]. It is well known that the double bonds of the diolefines are not coordinated perpendicular to the PRhP plane. The dihedral angle between the planes PRhP and XRhX (X = centroid of the double bond) is in the case of the (R,R)-COD-complex 5.6°(clockwise twist) and for the (R,R)-NBD-complex 5.3°(clockwise twist).

show abstract

Section: Discussionmentioning

confidence: 96%

Crystal structure of (η4-cycloocta-1,5-dien)-N-(2-(diphenylphosphinooxy)- 3-(naphthalen-1-yloxy)propyl)-N-(pentan-3-yl)-1,1-diphenylphosphinamine- rhodium(I) tetrafluoroborate, [Rh(C8H12)(C42H43NO2P2)][BF4]

Dai¹,

Heller²,

Preetz³

et al. 2007

Zeitschrift Für Kristallographie - New Crystal Structures

Self Cite

View full text Add to dashboard Cite

show abstract

“…The asymmetric hydrogenation of prochiral unsaturated compounds, such as olefins, imines, and ketones, provides a straightforward access to the corresponding optically active compounds, and has been extensively studied [1][2][3]. In contrast, the asymmetric hydrogenation of heteroaromatic compounds is much less explored [31][32][33][34][35].…”

Section: Asymmetric Hydrogenation Of Heteroaromaticsmentioning

confidence: 99%

“…The rhodium-catalyzed asymmetric hydrogenation is arguably one of the most powerful tools for the preparation of a wide range of enantiomerically pure or enriched compounds [1][2][3]. Although significant progress has been made in this area, the development of new phosphorus-containing ligands with properties superior to their predecessors remains a central task for chemists.…”

Section: Synthesis Of Chiral Phosphorus Ligandsmentioning

confidence: 99%

“…It was observed that a general drawback of Ir/P,P and Ir/N,P catalysts in the asymmetric hydrogenation reactions is the deactivation by the irreversible formation of inactive dimers and trimers through hybrid-bridged bonds in the presence of hydrogen gas [3,[40][41][42][43][44][45]. Thus, in iridium-catalyzed asymmetric hydrogenation of quinolines, the S/C ratios were usually limited to 100.…”

Section: Transitional Metal Catalyzed Asymmetric Hydrogenation Of Quimentioning

confidence: 99%

See 1 more Smart Citation

Adventure in Asymmetric Hydrogenation: Synthesis of Chiral Phosphorus Ligands and Asymmetric Hydrogenation of Heteroaromatics

Wang

et al. 2011

Asymmetric Catalysis From a Chinese Perspective

View full text Add to dashboard Cite

Catalytic asymmetric hydrogenations of prochiral unsaturated compounds, such as olefins, ketones, and imines, have been intensively studied and are considered as a versatile method of the synthesis of chiral compounds due to atom economy and operational simplicity. Since 2002, we mainly focused on synthesis of new phosphorus ligands, asymmetric hydrogenation of heteroaromatic compounds and palladium-catalyzed asymmetric hydrogenation. Significant contribution was made in the Dalian Institute of Chemical Physics. In this chapter, we hope to share our experience and adventure in the development of chiral monophosphite ligands and phosphine-phosphoramidite ligands, asymmetric hydrogenation of heteroaromatic compounds, and the development of new homogeneous palladium catalytic hydrogenation system, which have a wide range of applications in synthesis of chiral compounds.

show abstract

“…In comparison to PC, the reaction was more sluggish but still faster than in the other solvents. In relation to the known effect of longer overall reaction times with precatalysts bearing 1,5-cyclooctadiene (cod) as the stabilizing counter ligand in comparison to norbornadiene (nbd), [21,26] we used also the corresponding nbd complex. With this precatalyst in hand, the overall reaction time could be slightly diminished (Table 2, entries 9, 10) at 1 bar H 2 pressure.…”

mentioning

confidence: 99%

Rh‐Catalyzed Asymmetric Hydrogenation of Unsaturated Lactate Precursors in Propylene Carbonate

et al. 2008

View full text Add to dashboard Cite

The asymmetric hydrogenation of alpha-acetoxy acrylates to O-acetyl lactates with Rh catalysts based on chiral bisphospholane ligands was investigated in propylene carbonate (PC) as "green" solvent. In contrast to DuPHOS-type ligands, catASium M ligands lead to full conversion of the substrate in PC and induce excellent enantioselectivities for ethyl ester and methyl ester substrates (>98 %). Moreover, the undesired opening of the maleic anhydride moiety of the catASium M ligand observed in MeOH can be prevented under these conditions. The chiral product can be easily separated from the carbonate solvent by distillation. In this way, an ecologically benign process for the production of enantiopure lactic acid derivatives was established which offers a highly efficient catalytic transformation in a green solvent under mild conditions (1-10 bar H(2)).

show abstract

Catalyst Inhibition and Deactivation in Homogeneous Hydrogenation

Cited by 32 publications

References 108 publications

Crystal structure of (η4-cycloocta-1,5-dien)-N-(2-(diphenylphosphinooxy)- 3-(naphthalen-1-yloxy)propyl)-N-(pentan-3-yl)-1,1-diphenylphosphinamine- rhodium(I) tetrafluoroborate, [Rh(C8H12)(C42H43NO2P2)][BF4]

Crystal structure of (η4-cycloocta-1,5-dien)-N-(2-(diphenylphosphinooxy)- 3-(naphthalen-1-yloxy)propyl)-N-(pentan-3-yl)-1,1-diphenylphosphinamine- rhodium(I) tetrafluoroborate, [Rh(C8H12)(C42H43NO2P2)][BF4]

Adventure in Asymmetric Hydrogenation: Synthesis of Chiral Phosphorus Ligands and Asymmetric Hydrogenation of Heteroaromatics

Rh‐Catalyzed Asymmetric Hydrogenation of Unsaturated Lactate Precursors in Propylene Carbonate

Contact Info

Product

Resources

About