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Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule02:17

Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule

18.3K
If a set of reactants can yield multiple constitutional isomers, but one of the isomers is obtained as the major product, the reaction is said to be regioselective. In such reactions, bond formation or breaking is favored at one reaction site over others.
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...
18.3K
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation02:24

Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation

9.4K
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.
9.4K
Radical Anti-Markovnikov Addition to Alkenes: Overview01:25

Radical Anti-Markovnikov Addition to Alkenes: Overview

4.4K
The addition of hydrogen bromide to alkenes in the presence of hydroperoxides or peroxides proceeds via an anti-Markovnikov pathway and yields alkyl bromides.
4.4K
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation02:17

Reduction of Alkenes: Asymmetric Catalytic Hydrogenation

4.0K
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...
4.0K
Preparation of Alkynes: Alkylation Reaction02:27

Preparation of Alkynes: Alkylation Reaction

12.6K
Introduction
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
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Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation02:47

Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation

21.8K
Introduction
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
21.8K

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Updated: Mar 25, 2026

A Two-Step Protocol for Umpolung Functionalization of Ketones Via Enolonium Species
08:12

A Two-Step Protocol for Umpolung Functionalization of Ketones Via Enolonium Species

Published on: August 16, 2018

10.7K

Remote functionalization through alkene isomerization.

Alexandre Vasseur1, Jeffrey Bruffaerts1, Ilan Marek1

  • 1The Mallat Family Laboratory of Organic Chemistry, Schulich Faculty of Chemistry and the Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa, 32000 Israel.

Nature Chemistry
|February 20, 2016
PubMed
Summary

This review explores remote functionalization of alkenes using metal complexes to achieve selective reactions at distal positions. This metal-assisted strategy offers a powerful new approach for complex molecule synthesis.

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Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
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A Microwave-Assisted Direct Heteroarylation of Ketones Using Transition Metal Catalysis
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A Microwave-Assisted Direct Heteroarylation of Ketones Using Transition Metal Catalysis

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Area of Science:

  • Organic Chemistry
  • Catalysis
  • Synthetic Methodology

Background:

  • Achieving selective reactivity at distant sites within a molecule is a significant challenge in organic synthesis.
  • Remote functionalization, particularly in flexible acyclic systems, remains difficult due to the distance between functional groups.
  • Developing efficient methods for remote functionalization is crucial for accessing diverse molecular derivatives.

Purpose of the Study:

  • To review the concept of remote functionalization of alkenes mediated by metal complexes.
  • To highlight the potential of using the alkene double bond as a chemical handle for long-distance activation.
  • To showcase the synthetic opportunities offered by metal-assisted remote functionalization strategies.

Main Methods:

  • Discussion of remote functionalization strategies involving metal complexes.
  • Focus on selective reactions occurring at positions distal to the initial alkene.
  • Presentation of selected and representative examples to illustrate the methodology.

Main Results:

  • Demonstration of metal complexes enabling selective functionalization at positions remote from the alkene.
  • Evidence of the alkene's utility as a directing group for metal-catalyzed remote reactions.
  • Successful application of long-distance activation strategies in various synthetic contexts.

Conclusions:

  • Metal-assisted remote functionalization of alkenes represents a powerful and versatile synthetic strategy.
  • This approach overcomes limitations associated with traditional methods for functionalizing distant molecular sites.
  • The field offers vast opportunities for the synthesis of complex organic molecules and derivatives.