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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.
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The carbonyl carbon in an aldehyde or ketone is the site of a nucleophilic attack due to its electron-deficient nature. Depending on the strength of the incoming nucleophile, the reaction occurs via different mechanistic pathways.
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Kinetic Studies and Significance
In a chemical reaction, a relationship exists between the concentration of reactants and the rate at which the reaction proceeds. The study to measure this relationship is known as the kinetics of a chemical reaction. Kinetic studies are used to deduce the rate law of a chemical reaction, which provides information about the species involved during the transition state of the rate-determining step. Thus, kinetic studies help to derive the mechanism of a...
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Historical perspective
In 1896, the German chemist Paul Walden discovered that he could interconvert pure enantiomeric (+) and (-) malic acids through a series of reactions. This conversion suggested the involvement of optical inversion during the substitution reaction. Further, in 1930, Sir Christopher Ingold described for the first time two different forms of nucleophilic substitution reactions, which are known as SN1 (nucleophilic substitution unimolecular) and SN2 (nucleophilic substitution...
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Simple aryl halides do not react with nucleophiles. However, nucleophilic aromatic substitutions can be forced under certain conditions, such as high temperatures or strong bases. The mechanism of substitution under such conditions involves the highly unstable and reactive benzyne intermediate. Benzyne contains equivalent carbon centers at both ends of the triple bond, each of which is equally susceptible to nucleophilic attack. This 50–50 distribution of products is...
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Nucleophilic Addition versus Migratory Insertion Pathways in the Gold-Catalyzed Heck Reaction: A Computational Study.

Peter H M Budzelaar1, Luca Rocchigiani2, Manfred Bochmann3

  • 1Department of Chemistry, University of Naples Federico II, Via Cintia, Naples, I-80126, Italy.

Chemistry (Weinheim an Der Bergstrasse, Germany)
|June 25, 2025
PubMed
Summary

Computational studies reveal that nucleophilic attack is the favored pathway in gold(III)-catalyzed Heck-type reactions. Alkene insertion is less favorable, even with modified ligands, and 1,2-insertion is preferred over 2,1-insertion.

Keywords:
DFTcatalysischelate ligandsgoldmechanisms

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Area of Science:

  • Organometallic Chemistry
  • Catalysis
  • Computational Chemistry

Background:

  • The Heck reaction is a crucial carbon-carbon bond-forming reaction in organic synthesis.
  • Gold catalysis offers an alternative to traditional palladium catalysts for Heck-type reactions.
  • Understanding the reaction mechanism is vital for catalyst design and optimization.

Purpose of the Study:

  • To computationally investigate the initial reaction steps in P^N chelated Au(III) catalyzed Heck-type arylated alkene formation.
  • To compare two mechanistic pathways: alkene coordination/insertion and nucleophilic attack.
  • To elucidate the influence of ligand structure and steric hindrance on the reaction mechanism and regioselectivity.

Main Methods:

  • Density Functional Theory (DFT) calculations were employed to model the reaction pathways.
  • Two main mechanistic alternatives were explored: alkene insertion into a gold-carbon bond and nucleophilic attack on a gold(III) alkene adduct.
  • The effects of varying alkene substrates and ligand substituents (P^N and P^P chelates) were analyzed.

Main Results:

  • The nucleophilic attack pathway was found to be energetically favored over alkene insertion for P^N chelated Au(III) complexes.
  • Ligand trans-influence significantly governs reaction pathways, while steric effects show minimal impact.
  • Switching to a P^P chelate destabilizes the Au-Ph bond, making alkene insertion competitive, with a preference for 1,2-insertion regiochemistry.

Conclusions:

  • The study rules out an alkene insertion pathway for the formation of Heck-type olefins catalyzed by the investigated Au(III) complexes.
  • Nucleophilic attack is the dominant mechanism under the studied conditions.
  • Catalyst design, particularly ligand choice (P^N vs. P^P), can influence the relative importance of different mechanistic pathways.