Industrial Catalysts for Regio‐ or Stereo‐Selective Oxidations and Reductions. A Review of Key Technologies and Targets

Whittall, John

doi:10.1002/9780470090244.ch1

Cited by 3 publications

(1 citation statement)

References 67 publications

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“…This is most famously exemplified by the selective oxidation of methane to methanol, a natural process that is not practiced on an industrial scale because there are no known catalysts that can selectively react with the C–H bonds in methane but not those in methanol with sufficient activity . Other targets of industrial interest abound and include aromatic oxidations, benzylic oxidations, and olefin epoxidations . Indeed, oxygenates represent some of the most versatile commodity chemicals, , justifying the continued interest in the discovery of new selective oxidation catalysts from both a fundamental and an applied perspective .…”

Section: Introductionmentioning

confidence: 99%

Selective Catalytic Olefin Epoxidation with Mn^II-Exchanged MOF-5

et al. 2017

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Partial substitution of Zn II by Mn II in Zn4O-(terephthalate)3 (MOF-5) leads to a distorted all-oxygen ligand field supporting a single Mn II site, whose structure was confirmed by Mn K-edge X-ray absorption spectroscopy. The Mn II ion at the MOF-5 node engages in redox chemistry with a variety of oxidants. With t BuSO2PhIO, it produces a putative Mn IVoxo intermediate, which upon further reaction with adventitious hydrogen is trapped as a Mn III −OH species. Most intriguingly, the intermediacy of the high-spin Mn IV −oxo species is likely responsible for catalytic activity of the Mn II-MOF-5 precatalyst, which in the presence of t BuSO2PhIO catalyzes oxygen atom transfer reactivity to form epoxides from cyclic alkenes with >99% selectivity. These results demonstrate that MOF secondary building units serve as competent platforms for accessing terminal high-valent metal−oxo species that consequently engage in catalytic oxygen atom transfer chemistry owing to the relatively weak ligand fields provided by the SBU.

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Section: Introductionmentioning

confidence: 99%

Selective Catalytic Olefin Epoxidation with Mn^II-Exchanged MOF-5

et al. 2017

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A Versatile Ru Catalyst for the Asymmetric Transfer Hydrogenation of Both Aromatic and Aliphatic Sulfinylimines

Pablo

Guijarro

Kovács

et al. 2012

Chemistry A European J

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A highly efficient Ru catalyst based on an achiral, very simple, and inexpensive amino alcohol ligand (2-amino-2-methylpropan-1-ol) has been developed for the asymmetric transfer hydrogenation (ATH) of chiral N-(tert-butylsulfinyl)imines. This complex is able to catalyze the ATH of both aromatic and the most challenging aliphatic sulfinylimines by using isopropyl alcohol as the hydrogen source. The diastereoselective reduction of aromatic, heteroaromatic, and aliphatic sulfinylketimines, including sterically congested cases, over short reaction times (1-4 h), followed by desulfinylation of the nitrogen atom, affords the corresponding highly enantiomerically enriched (ee up to >99 %) α-branched primary amines in excellent yields. The same ligand was equally effective for the synthesis of both (R)- and (S)-amines by using the appropriate absolute configuration in the iminic substrate. DFT mechanistic studies show that the hydrogen-transfer process is stepwise. Moreover, the origin of the diastereoselectivity has been rationalized.

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Synthesis, Coordination Behavior, and Use in Asymmetric Hydrogenations of Walphos-Type Ligands

et al. 2008

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A total of nine Walphos-type diphosphine ligands, all of which have a ferrocenyl-aryl backbone, have been synthesized, characterized, and tested in asymmetric ruthenium-, rhodium-, and iridium-catalyzed hydrogenations of alkenes, ketones, and one imine. Ruthenium- and rhodium-mediated hydrogenations of alkenes and ketones gave enantioselectivities of up to 95% and 97% ee, respectively. Ligand tuning was attempted by variation of the phosphorus-bound aryl and alkyl substituents and by attaching electron-donating or electron-withdrawing substituents to the backbone phenyl ring. Dichloropalladium(II) complexes of five ligands were synthesized, and in four cases the molecular structures were studied in solution as well as in the solid state.

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Industrial Catalysts for Regio‐ or Stereo‐Selective Oxidations and Reductions. A Review of Key Technologies and Targets

Cited by 3 publications

References 67 publications

Selective Catalytic Olefin Epoxidation with Mn^II-Exchanged MOF-5

Selective Catalytic Olefin Epoxidation with Mn^II-Exchanged MOF-5

A Versatile Ru Catalyst for the Asymmetric Transfer Hydrogenation of Both Aromatic and Aliphatic Sulfinylimines

Synthesis, Coordination Behavior, and Use in Asymmetric Hydrogenations of Walphos-Type Ligands

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Industrial Catalysts for Regio‐ or Stereo‐Selective Oxidations and Reductions. A Review of Key Technologies and Targets

Cited by 3 publications

References 67 publications

Selective Catalytic Olefin Epoxidation with MnII-Exchanged MOF-5

Selective Catalytic Olefin Epoxidation with MnII-Exchanged MOF-5

A Versatile Ru Catalyst for the Asymmetric Transfer Hydrogenation of Both Aromatic and Aliphatic Sulfinylimines

Synthesis, Coordination Behavior, and Use in Asymmetric Hydrogenations of Walphos-Type Ligands

Contact Info

Product

Resources

About

Selective Catalytic Olefin Epoxidation with Mn^II-Exchanged MOF-5

Selective Catalytic Olefin Epoxidation with Mn^II-Exchanged MOF-5