Synthesis and Reactive Intermediates
| Code | School | Level | Credits | Semesters |
| CHEM3065 | Chemistry | 3 | 20 | Full Year UK |
- Code
- CHEM3065
- School
- Chemistry
- Level
- 3
- Credits
- 20
- Semesters
- Full Year UK
Summary
Palladium catalysis in organic synthesis - Tsuji-Trost pi-allyl chemistry, Heck and Stille reaction, Suzuki, Buchwald-Hartwig and Sonagashira coupling, C-H Activation, etc, with illustrative examples in synthesis.
Selectivity issues in organic synthesis Overview of reactivity principles. Synthesis of organometallics (mainly organolithiums) via metal-halogen exchange, metallation etc., including special methods of unsaturated types (Shapiro reaction, ortho-metallation) and heterosubstituted systems. Connective C=C bond formation, including Julia and Peterson olefinations (synthesis examples) and use of sulfur ylides for epoxidation and cyclopropanation. Cuprate chemistry, centred on conjugate addition-electrophilic quench sequences (regiospecfic enolates), but also including carbocupration and substitution. Protecting groups revisited, synthesis of amino acids and peptides. Stereochemistry revised, and an introduction to asymmetric synthesis, including chiral pool, chiral reagents, chial auxiliaries for enolate alkylation and amine synthesis, and catalytic asymmetric oxidation and reduction.
Use of frontier molecular orbital analysis to explain and predict stereochemical and regiochemical outcomes of pericyclic reactions (Woodward-Hoffmann rules etc). Examples will be drawn from (1) cycloadditions [4+2] (e.g. Diels-Alder, 1,3-dipolar), and [2+2]; (2) Electrocyclization reactions and selectivity rules under thermal and photochemical conditions; (3) Sigmatropic rearrangements (e.g. [3,3]- Claisen and Cope; [2,3]-Wittig, [2,3]-Still-Wittig and Mislow-Evans).
Generation and use of reactive intermediates in synthesis (i.e. radicals, carbenes, nitrenes, and arynes). Miscellaneous rearrangement reactions to electron-deficient carbon, nitrogen or oxygen.
Target Students
BSc/MSci Chemistry OR Medicinal and Biological Chemistry OR Chemistry and Molecular Physics OR Natural Sciences AND for Level 3 students.
Classes
- Two 1-hour workshops each week for 2 weeks
- One 1-hour tutorial each week for 4 weeks
- Two 1-hour lectures each week for 20 weeks
Assessment
- 100% Written exam (3-hour): Second re-assessment: If a further re-assessment is allowed by satisfying the conditions of Undergraduate Course Regulation 19, the form of the further re-assessment for this module will be 100% coursework.
Assessed by end of spring semester
Educational Aims
To show how modern palladium-mediated cross-coupling reactions can be used to synthesise useful organic molecules. To introduce students to a range of reagents and synthetic methodology, and to describe how it is applied to the synthesis of organic target molecules. How the use of protecting groups can enable complex molecule synthesis. To consolidate and develop concepts of organic reactivity and mechanism, primarily using qualitative frontier molecular orbital theory. To illustrate and rationalise molecular rearrangements in organic chemistry. To give an appreciation of the generation and use of reactive intermediates in organic chemistry.Learning Outcomes
Knowledge and Understanding: An understanding of the mechanisms, regiocontrol and stereochemical outcome of organic reactions.
Intellectual Skills: The ability to predict the regiochemical and stereochemical outcome of organic reactions.
Intellectual Skills: The ability to use organometallics to create organic structures.
Knowledge and Understanding: An understanding of the mechanisms, regiocontrol and stereochemical outcome of organic reactions.
Intellectual Skills: The ability to predict the regiochemical and stereochemical outcome of organic reactions.
Intellectual Skills: The ability to use pericyclic reactions, molecular rearrangements and reactive intermediates to create organic structures.
Transferable Skills: Problem-solving and written communication skills.
Conveners
- Prof Christopher James Hayes