Pericyclic Reactions

Outline for Online Book Sections on Pericyclic Reactions

1. Introduction to Pericyclic Reactions

  • Definition and key characteristics of pericyclic reactions.

  • Importance in organic synthesis and natural processes.

  • Overview of the three main types: electrocyclic reactions, cycloadditions, and sigmatropic rearrangements.


2. Electrocyclic Reactions

  • 2.1 Overview

    • Definition and examples (e.g., ring opening/closing reactions).

    • Stereochemical outcomes (conrotatory vs. disrotatory).

  • 2.2 Approaches to Analyze Electrocyclic Reactions

    • 2.2.1 Correlation Diagrams

      • Explanation of how to construct correlation diagrams for electrocyclic reactions.

      • Use of molecular orbital symmetry to predict outcomes.

    • 2.2.2 Hückel and Möbius Transition State Aromaticity Classification

      • Explanation of aromatic transition state theory.

      • Determining if the transition state is Hückel (4n+2 π-electrons) or Möbius (4n π-electrons).

    • 2.2.3 Frontier Orbital

      • Application of Woodward-Hoffmann rules to determine if a reaction is thermally or photochemically allowed from frontier orbitals.

  • Examples of allowed and forbidden electrocyclic reactions.2.3 Summary

    • Recap of key concepts and examples.


3. Cycloaddition Reactions

  • 3.1 Overview

    • Definition and examples (e.g., Diels-Alder reaction, [2+2] cycloaddition).

    • Classification based on the number of π-electrons involved.

  • 3.2 Approaches to Analyze Cycloaddition Reactions

    • 3.2.1 Correlation Diagrams

      • Construction of correlation diagrams for cycloaddition reactions.

      • Analysis of orbital symmetry interactions.

    • 3.2.2 Hückel and Möbius Transition State Classification

      • Identifying the topology of the transition state (Hückel or Möbius).

      • Determining aromaticity or antiaromaticity of the transition state.

    • 3.2.3 Allowed vs. Forbidden Reactions

      • Examples of allowed and forbidden electrocyclic reactions.Application of Woodward-Hoffmann rules to cycloadditions.

      • Examples of thermally and photochemically allowed cycloadditions.

  • 3.3 Summary

    • Recap of key concepts and examples.


4. Sigmatropic Rearrangements

  • 4.1 Overview

    • Definition and examples (e.g., [1,5]-H shift, Cope rearrangement).

    • Classification based on the number of atoms involved in the shift.

  • 4.2 Approaches to Analyze Sigmatropic Rearrangements

    • 4.2.1 Correlation Diagrams

      • Construction of correlation diagrams for sigmatropic rearrangements.

      • Analysis of orbital symmetry and migration patterns.

    • 4.2.2 Hückel and Möbius Transition State Classification

      • Determining the topology of the transition state (Hückel or Möbius).

      • Application to sigmatropic shifts.

    • 4.2.3 Allowed vs. Forbidden Reactions

      • Application of Woodward-Hoffmann rules to sigmatropic rearrangements.

      • Examples of allowed and forbidden sigmatropic shifts.

  • 4.3 Summary

    • Recap of key concepts and examples.


5. General Summary and Applications

  • Comparison of the three types of pericyclic reactions.

  • Importance of symmetry and orbital interactions in predicting reaction outcomes.

  • Real-world applications in organic synthesis, materials science, and biochemistry.


6. References and Further Reading

  • Key textbooks and papers on pericyclic reactions.

  • Online resources for further exploration.


Notes for Students

  • Use clear, concise language and include diagrams to illustrate concepts (e.g., correlation diagrams, molecular orbitals).

  • Provide specific examples for each type of reaction and approach.

  • Highlight the practical implications of understanding these reactions.

  • You could use vitamin D as an example of a electrocyclization and 1,7 hydride shift