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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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Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation02:24

Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation

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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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Ziegler–Natta Chain-Growth Polymerization: Overview01:17

Ziegler–Natta Chain-Growth Polymerization: Overview

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Ziegler–Natta polymerization is another form of addition or chain‐growth polymerization used for synthesizing linear polymers over branched polymers. The catalyst used for polymerization is the Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, who developed it in 1953. This catalyst is an organometallic complex of titanium tetrachloride and triethyl aluminum, with the active form of the catalyst being an alkyl titanium compound. Using the Ziegler–Natta...
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Reduction of Alkenes: Catalytic Hydrogenation02:13

Reduction of Alkenes: Catalytic Hydrogenation

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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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Catalysis02:50

Catalysis

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The presence of a catalyst affects the rate of a chemical reaction. A catalyst is a substance that can increase the reaction rate without being consumed during the process. A basic comprehension of a catalysts’ role during chemical reactions can be understood from the concept of reaction mechanisms and energy diagrams.
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Thermal Electrocyclic Reactions: Stereochemistry01:17

Thermal Electrocyclic Reactions: Stereochemistry

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The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
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Updated: Nov 17, 2025

Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks MOFs
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Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks MOFs

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Heavier Tetrylenes as Single Site Catalysts.

Nilanjana Sen1, Shabana Khan1

  • 1Department of Chemistry, Indian Institute of Science Education and Research (IISER), Pune, Dr. Homi Bhabha Road, Pashan, Pune, 411008, India.

Chemistry, an Asian Journal
|February 15, 2021
PubMed
Summary

Low-valent group 14 compounds, or tetrylenes, are emerging as powerful single-site catalysts for organic synthesis. These silicon, germanium, and tin compounds enable key transformations, advancing main group catalysis.

Keywords:
CyanosilylationGermyleneHydroborationSilyleneStannylene

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Area of Science:

  • Main group chemistry
  • Organometallic chemistry
  • Catalysis

Background:

  • Compounds with heavier low-valent group 14 elements (tetrylenes) exhibit electronic properties similar to transition metals.
  • Tetrylenes possess stereochemically active lone pairs and accessible π-antibonding orbitals.
  • Small molecule activation by tetrylenes was known, but catalytic applications were a long-standing challenge.

Purpose of the Study:

  • To provide an overview of the development of tetrylenes as single-component catalysts in organic transformations.
  • To highlight recent methodologies utilizing silicon(II), germanium(II), and tin(II) compounds in catalysis.
  • To emphasize mechanistic investigations of these catalytic processes.

Main Methods:

  • Review of literature on low-valent group 14 compounds as catalysts.
  • Focus on methodologies for hydroboration, cyanosilylation, N-formylation, and dehydrocoupling reactions.
  • Emphasis on understanding reaction mechanisms through experimental and computational studies.

Main Results:

  • Numerous successful catalytic applications of Si(II), Ge(II), and Sn(II) compounds have been discovered.
  • These tetrylene catalysts are effective in various organic transformations, including hydroboration of carbonyls and pyridines.
  • Significant progress has been made in understanding the reaction pathways and catalytic cycles.

Conclusions:

  • Low-valent group 14 compounds are versatile and effective single-site catalysts for organic synthesis.
  • The unique electronic properties of tetrylenes facilitate diverse catalytic activities.
  • Continued research into tetrylene chemistry promises further advancements in main group catalysis.