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Reduction of Alkenes: Asymmetric Catalytic Hydrogenation02:17

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Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
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The rate of acid-catalyzed hydration of alkenes depends on the alkene's structure, as the presence of alkyl substituents at the double bond can significantly influence the rate.
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Reduction of Alkenes: Catalytic Hydrogenation02:13

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Alkenes undergo reduction by the addition of molecular hydrogen to give alkanes. Because the process generally occurs in the presence of a transition-metal catalyst, the reaction is called catalytic hydrogenation.
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
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Carboxylic Acids to Esters: Acid-Catalyzed (Fischer) Esterification Mechanism01:13

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Carboxylic acids react with alcohols to yield esters via an acid-catalyzed condensation reaction called Fischer esterification. This is a nucleophilic acyl substitution reaction that proceeds via a tetrahedral intermediate, where a water molecule is eliminated as the leaving group.
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Introduction
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Regioselectivity and Stereochemistry of Hydroboration02:36

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A significant aspect of hydroboration–oxidation is the regio- and stereochemical outcome of the reaction.
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Interfacial Proton-Coupled Electron Transfer Reverses Water Inhibition for Selective 5-hydroxymethylfurfural

Haopeng Pei1, Guangming Zhan2, Yinghao Li1

  • 1State Key Laboratory of Green Papermaking and Resource Recycling, School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai, P. R. China.

Angewandte Chemie (International Ed. in English)
|April 25, 2026
PubMed
Summary

Engineered nickel on nanoscale zero-valent iron (nZVI) enables efficient, selective hydrogenation of 5-hydroxymethylfurfural (HMF) in water. This breakthrough overcomes water layer inhibition, enhancing biomass valorization via proton-coupled electron transfer (PCET).

Keywords:
interfacial proton‐coupled electron transfernanoscale zero‐valent ironselective hydrogenationwater inhibition reversal

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Area of Science:

  • Catalysis
  • Materials Science
  • Biomass Valorization

Background:

  • Selective aqueous hydrogenation of 5-hydroxymethylfurfural (HMF) to 2,5-bis(hydroxymethyl)furan (BHMF) is crucial for converting biomass into valuable chemicals.
  • Nanoscale zero-valent iron (nZVI) is a promising H2-free hydrogenation catalyst, but its performance is limited by a rigid interfacial water layer that hinders substrate access and selectivity.

Purpose of the Study:

  • To overcome the limitations of nZVI in aqueous hydrogenation by engineering its surface properties.
  • To develop a novel catalytic system for efficient and selective HMF hydrogenation using a proton-coupled electron transfer (PCET) mechanism.

Main Methods:

  • Atomically dispersed Ni sites were engineered onto nZVI.
  • The mechanism involved electron-deficient Ni (Niδ+) acting as electron pumps and facilitating proton transfer.
  • Niδ+ induced electronic modulation of Fe sites to create a proton shuttle.

Main Results:

  • The engineered Ni/nZVI catalyst achieved a significantly enhanced electron selectivity of 81.6% for BHMF production, compared to 10.6% for pristine nZVI.
  • High HMF conversion (>95%) and BHMF selectivity (>95%) were obtained under ambient conditions for concentrations ranging from 20-150 mM.
  • The catalytic system demonstrated a performance orders of magnitude better than pristine nZVI, which showed <10% conversion.

Conclusions:

  • Engineering interfacial PCET pathways by dispersing Ni atoms on nZVI effectively reverses solvent inhibition in aqueous hydrogenation.
  • This approach provides a general strategy for developing highly efficient and selective hydrogenation catalysts in aqueous media.
  • The study opens new avenues for sustainable biomass valorization and chemical synthesis.