The regioselective activation of C-H bonds and subsequent transformation into desirable functional groupS is an attractive prospect in organic synthesis. We have developed two novel C-H functionalisation reactions; the first is an intramolecular, sulfonamide directed, C-H amination reaction for the synthesis of 3_phenylisoindolinone derivates and the second is a sulfonamide directed ortho C-H acetoxylation reaction. Both isoindolinones and phenol derivatives of sulfonamides are important motifs in numerous pharmaceutically relevant compounds. The Cull-catalysed intramolecular C-H amination reaction for the synthesis of substituted 3-phenylisolindolinone derivatives (Scheme i) was found to be tolerant to substitution on both aromatic rings, however, no reaction was observed on exchanging the tethered aryl group for an alkyl group. Mechanistic investigations revealed that C-H cleavage was not part of the rate-determining step which is likely to be coordination of the copper catalyst to the sulfonyl amide. Substitution of the tethered phenyl ring (R2 ) and a subsequent Hammett analysis indicated that this coordination may be accelerated by a cation-IT interaction between CU11 and the pie system of the aryl group.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:685335 |
| Date | January 2015 |
| Creators | Bowen, John George |
| Publisher | University of Bristol |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
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