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Related Concept Videos

Transition State Theory01:25

Transition State Theory

Transition-state theory, also known as activated-complex theory, provides a molecular-level explanation of reaction rates in both gas-phase and solution-phase reactions. It extends earlier kinetic models by considering the formation of a short-lived, high-energy configuration during a reaction.The progress of a chemical reaction can be represented using a reaction profile, which plots potential energy against the reaction coordinate. As two reactant molecules approach one another, their...
Thermal Electrocyclic Reactions: Stereochemistry01:17

Thermal Electrocyclic Reactions: Stereochemistry

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.
Thermal and Photochemical Electrocyclic Reactions: Overview01:26

Thermal and Photochemical Electrocyclic Reactions: Overview

Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
Anionic Chain-Growth Polymerization: Mechanism01:04

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The mechanism for anionic chain-growth polymerization involves initiation, propagation, and termination steps. In the initiation step, a nucleophilic anion, such as butyl lithium, initiates the polymerization process by attacking the π bond of the vinylic monomer. As a result, a carbanion, stabilized by the electron‐withdrawing group, is generated. The resulting carbanion acts as a Michael donor in the propagation step and attacks the second vinylic monomer, which acts as a Michael acceptor.
Pericyclic Reactions: Introduction01:17

Pericyclic Reactions: Introduction

Pericyclic reactions are organic reactions that occur via a concerted mechanism without generating any intermediates. The reactions proceed through the movement of electrons in a closed loop to form a cyclic transition state, where rearrangement of the σ and π bonds yields specific products.
Pericyclic reactions can be classified into three categories: electrocyclic reactions, cycloaddition reactions, and sigmatropic rearrangements. Electrocyclic reactions and sigmatropic rearrangements are...
Cationic Chain-Growth Polymerization: Mechanism00:57

Cationic Chain-Growth Polymerization: Mechanism

The cationic polymerization mechanism consists of three steps: initiation, propagation, and termination. In the initiation step of the polymerization process, the π bond of a monomer gets protonated by the Lewis acid catalyst, which is formed from boron trifluoride and water. The protonation of the π bond generates a carbocation stabilized by the electron‐donating group. In the propagation step, the π bond of the second monomer acts as a nucleophile and attacks the generated carbocation,...

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Unraveling Entropic Rate Acceleration Induced by Solvent Dynamics in Membrane Enzymes
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Kinetic analysis for macrocyclizations involving anionic template at the transition state.

Vicente Martí-Centelles1, M Isabel Burguete, Santiago V Luis

  • 1Departamento de Química Inorgánica y Orgánica, Universitat Jaume I, E12071 Castellón de la Plana, Spain.

Thescientificworldjournal
|June 6, 2012
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Summary

New kinetic models analyze C₂ pseudopeptide macrocyclization via S(N)2 reactions, considering byproduct formation and anion catalysis for process optimization.

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Area of Science:

  • Organic Chemistry
  • Chemical Kinetics

Background:

  • Macrocyclization reactions are crucial for synthesizing complex molecules.
  • Understanding reaction kinetics is vital for optimizing chemical processes.
  • Oligomerization/polymerization can compete with desired macrocyclization.

Purpose of the Study:

  • To develop kinetic models for C₂ pseudopeptide macrocyclization.
  • To incorporate competitive oligomerization/polymerization into models.
  • To investigate the catalytic role of anions in the S(N)2 reaction.

Main Methods:

  • Development of several kinetic models.
  • Numerical solution of differential equation systems.
  • Analysis of reaction parameters and byproduct formation.

Main Results:

  • Models account for both macrocyclization and polymerization.
  • Anion effects on transition state stabilization are modeled.
  • Numerical solutions provide insights into reaction mechanisms.

Conclusions:

  • Developed models enhance understanding of macrocyclization kinetics.
  • Insights facilitate optimization strategies for desired macrocycle synthesis.
  • Kinetic modeling aids in controlling byproduct formation.