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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...

Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation

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Introduction
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In organic synthesis, the formation of products can be altered by changing the reaction conditions. For example, a dibromo addition product is formed when propene is treated with bromine at room temperature. In contrast, propene undergoes allylic substitution in non-polar solvents at high temperatures to give 3-bromopropene. In order to avoid the addition reaction, the bromine concentration must be kept as low as possible throughout the reaction. This can be achieved using N-bromosuccinimide...

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The addition of hydrogen bromide to alkenes in the presence of hydroperoxides or peroxides proceeds via an anti-Markovnikov pathway and yields alkyl bromides.

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Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions

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Published on: July 30, 2017

Catalyst Deactivation During Rhodium Complex-Catalyzed Propargylic C-H Activation.

Saskia Möller¹, Nora Jannsen¹, Julia Rüger¹

¹Leibniz-Institut für Katalyse e.V., Albert-Einstein-Str. 29a, 18059, Rostock, Germany.

Chemistry (Weinheim an Der Bergstrasse, Germany)

|July 14, 2021

Summary

Researchers detailed the mechanism of rhodium-catalyzed propargylic C-H activation for synthesizing branched allylic esters. This led to an optimized, more active catalytic system for improved ester synthesis.

Keywords:

C−H activation catalyst deactivation concentration diagrams kinetics rhodium catalysis

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Published on: April 10, 2015

Area of Science:

Organic Chemistry
Catalysis
Reaction Mechanism

Background:

Previously reported synthesis of branched allylic esters via rhodium complex-catalyzed propargylic C-H activation.
Need for detailed mechanistic understanding to optimize the catalytic system.

Purpose of the Study:

To conduct detailed mechanistic investigations of the reaction.
To characterize intermediate formation under reaction conditions.
To optimize the catalytic system for enhanced activity.

Main Methods:

Utilized various analytical techniques including Nuclear Magnetic Resonance (NMR), X-ray crystal structure analysis, and Raman spectroscopy.
Employed kinetic methods to study reaction intermediates.
Applied mechanistic insights to optimize reaction conditions.

Main Results:

Characterized key intermediates formed during the catalytic cycle.
Gained a deeper understanding of the propargylic C-H activation mechanism.
Developed an optimized catalytic system with significantly improved activity.

Conclusions:

Detailed mechanistic studies provide crucial insights into rhodium-catalyzed propargylic C-H activation.
Optimization based on mechanistic understanding leads to a more active and efficient catalytic system for branched allylic ester synthesis.