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CHY8422 : Pericyclic and radical reactions

  • Offered for Year: 2022/23
  • Module Leader(s): Dr Michael Hall
  • Lecturer: Dr Julian Knight
  • Owning School: Natural and Environmental Sciences
  • Teaching Location: Newcastle City Campus
Semester 1 Credit Value: 10
ECTS Credits: 5.0


To introduce and develop the concepts of thermal and photochemical pericyclic reactions and Frontier Molecular Orbital (FMO) theory; to describe the methods used to determine the mechanisms of such reactions; to discuss radical chemistry; to explore reactions involving radicals and ions in cyclisation reactions.

Outline Of Syllabus

Pericyclic reactions and Frontier Molecular Orbital Theory (FMO)

1-3 Molecular Orbitals and revision of the application of Frontier MO theory to ionic (and radical) processes and relevance to Hard and Soft Acid and Base theory.
Construction of basic FMO's for linear conjugated pi-systems.
Introduction to pericyclic reactions.
4-6 Cycloaddition reactions. The Diels-Alder reaction: mechanism, Frontier-Orbital analysis, stereospecificity. The effect of substituents on FMO energies and coefficients. Stereoselectivity and regioselectivity in Diels-Alder reactions. Cheletropic reactions and 1,3-dipolar cycloadditions. Photochemical cycloaddition reactions. The Woodward-Hoffmann rules.
7-8 Electrocyclic reactions.
9-11 Sigmatropic reactions. Group transfer reactions.
12 Revision lecture

Radical Reactions

1-2 Introduction to free radicals: generation of radicals (thermal, photochemical, electrochemical), properties and reactivity, SOMO, hard vs. soft.
3-4 Stoichiometric radical processes: removal of functional groups and other applications in synthesis.
5-7 Kinetics of radical reactions: chain reactions, polymerisation, the use of tin centred radicals, applications in synthesis, alternatives for tin.
8 Ring closing reactions: predicting ring closure with Baldwin’s rules and cascade processes.
9-11 Modern advances in radical chemistry
12 Revision lecture

Teaching Methods

Teaching Activities
Category Activity Number Length Student Hours Comment
Guided Independent StudyAssessment preparation and completion220:3011:00Revision for assessment
Structured Guided LearningLecture materials241:0024:00Lectures
Scheduled Learning And Teaching ActivitiesDrop-in/surgery41:004:00Online - 4 live meetings to be spread evenly through out semester 1
Guided Independent StudyIndependent study161:0061:00N/A
Jointly Taught With
Code Title
CHY8835Pericyclic and radical reactions
Teaching Rationale And Relationship

In online lecture materials students learn advanced concepts in the organic chemistry of reactions involving cyclic transition states and radical intermediates which, encompasses synthetic, theoretical and mechanistic principles.

Assessment Methods

The format of resits will be determined by the Board of Examiners

Description Length Semester When Set Percentage Comment
PC Examination1201A100Including computer based MCQ and long answers
Exam Pairings
Module Code Module Title Semester Comment
CHY8835Further Organic Chemistry1N/A
Assessment Rationale And Relationship

The alternate assessments will test the students’ knowledge and understanding of the content of this module in the context of both synthetic and mechanistic chemistry.

Study Abroad students may request to take their assessment before the semester 1 exam period, in which case the format of the paper may differ from that shown in the MOF. Study Abroad students should contact the school to discuss this.

Reading Lists