Asymmetric hydrogenation of an α-unsaturated carboxylic acid catalyzed by intact chiral transition metal carbonyl clusters - diastereomeric control of enantioselectivity

Twenty clusters of the general formula [(μ-H) 2 Ru 3 (μ 3 -S)(CO) 7 (μ-P-P*)] (P-P* = chiral diphosphine of the ferrocene-based Walphos or Josiphos families) have been synthesised and characterised. The clusters have been tested as catalysts for asymmetric hydrogenation of tiglic acid [ trans -2-met...

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Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2020-04, Vol.49 (14), p.4244-4256
Main Authors: Abdel-Magied, Ahmed F, Theibich, Yusuf, Singh, Amrendra K, Rahaman, Ahibur, Doverbratt, Isa, Raha, Arun K, Haukka, Matti, Richmond, Michael G, Nordlander, Ebbe
Format: Article
Language:English
Subjects:
Asymmetry
Carbon monoxide
Carbonyls
Carboxylic acids
Catalysts
Catalytic converters
Chemical Sciences
Clusters
Crystallography
Enantiomers
Fysikalisk kemi
Hydrogenation
Kemi
Natural Sciences
Naturvetenskap
NMR
Nuclear magnetic resonance
Physical Chemistry
Transition metals
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Summary:Twenty clusters of the general formula [(μ-H) 2 Ru 3 (μ 3 -S)(CO) 7 (μ-P-P*)] (P-P* = chiral diphosphine of the ferrocene-based Walphos or Josiphos families) have been synthesised and characterised. The clusters have been tested as catalysts for asymmetric hydrogenation of tiglic acid [ trans -2-methyl-2-butenoic acid]. The observed enantioselectivities and conversion rates strongly support catalysis by intact Ru 3 clusters. A catalytic mechanism involving an active Ru 3 catalyst generated by CO loss from [(μ-H) 2 Ru 3 (μ 3 -S)(CO) 7 (μ-P-P*)] has been investigated by DFT calculations. Asymmetric hydrogenation catalysis by [(μ-H) 2 Ru 3 (μ 3 -S)(CO) 7 (μ-P-P*)] (P-P* = chiral diphosphine) indicates intact chiral clusters as active catalysts.
ISSN:1477-9226
1477-9234
DOI:10.1039/c9dt04799a