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Reduction of Alkenes: Asymmetric Catalytic Hydrogenation02:17

Reduction of Alkenes: Asymmetric Catalytic Hydrogenation

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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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Acid halides are reduced to alcohols in the presence of a strong reducing agent like lithium aluminum hydride.
The mechanism proceeds in three steps. First, the nucleophilic hydride ion attacks the carbonyl carbon of the acid halide to form a tetrahedral intermediate. Next, the carbonyl group is re-formed, and the halide ion departs as a leaving group, generating an aldehyde. A second nucleophilic attack by the hydride yields an alkoxide ion, which, upon protonation, gives a primary alcohol as...
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Introduction
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
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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.
The hydrogenation process takes place on the...
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Alcohols from Carbonyl Compounds: Reduction02:23

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Reduction is a simple strategy to convert a carbonyl group to a hydroxyl group. The three major pathways to reduce carbonyls to alcohols are catalytic hydrogenation, hydride reduction, and borane reduction.
Catalytic hydrogenation is similar to the reduction of an alkene or alkyne by adding H2 across the pi bond in the presence of transition metal catalysts like Raney Ni, Pd–C, Pt, or Ru. Aldehydes and ketones can be reduced by this method, often under mild to moderate heat (25–100°C) and...
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Carboxylic Acids to Primary Alcohols: Hydride Reduction01:17

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Carboxylic acids, upon reaction with strong reducing agents such as lithium aluminum hydride followed by hydrolysis, undergo reduction to form primary alcohols.
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Light-Responsive Aldehyde-Reduction Catalysis Through Catalyst Encapsulation.

Amit Ghosh1, John D Thoburn2, Jonathan R Nitschke1

  • 1Yusuf Hamied Department of Chemistry, University of Cambridge, Cambridge, CB2 1EW, United Kingdom.

Angewandte Chemie (International Ed. in English)
|November 12, 2024
PubMed
Summary
This summary is machine-generated.

Researchers developed a light-responsive metal-organic capsule for a perrhenate catalyst. This capsule releases the catalyst with UV light to enable organic carbonyl reduction, and reforms with heat, allowing for multiple on-off catalytic cycles.

Keywords:
Supramolecular chemistrycoordination capsulesphoto-switchable cagessubcomponent self-assemblyswitchable catalysis

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Area of Science:

  • Supramolecular Chemistry
  • Catalysis
  • Materials Science

Background:

  • Metal-organic frameworks (MOFs) offer tunable structures for host-guest chemistry.
  • Controlling catalyst activity with external stimuli is crucial for advanced chemical processes.
  • Photochemical control over catalytic reactions remains an area of active research.

Purpose of the Study:

  • To design and synthesize a light-responsive metal-organic capsule.
  • To investigate the controlled release and re-encapsulation of a perrhenate catalyst.
  • To demonstrate light-triggered catalytic activity for organic carbonyl reduction.

Main Methods:

  • Synthesis of a tetrahedral metal-organic capsule.
  • Encapsulation of a perrhenate catalyst within the capsule.
  • Photochemical release of the catalyst using 350 nm light.
  • Catalytic reduction of organic carbonyls using hydrosilanes.
  • Thermal treatment for catalyst re-encapsulation.

Main Results:

  • The capsule selectively releases the perrhenate catalyst upon 350 nm light irradiation.
  • The released catalyst efficiently promotes the reduction of organic carbonyls by hydrosilanes.
  • Catalytic activity is switched off by heating at 75°C for 2.5 hours, leading to catalyst re-encapsulation.
  • Multiple on-off cycles of catalysis were demonstrated, correlating product yield with light exposure time.

Conclusions:

  • Encapsulation provides a platform for coupling light-responsiveness with catalysis.
  • This system demonstrates reversible control over catalytic activity via light and heat.
  • The strategy may be generalizable to other catalysts and metal-organic capsules for diverse applications.