An Investigation into the Smiles Rearrangement, and other studies

Abstract

Rearrangement reactions are useful tools in organic synthesis. The Smiles Rearrangement is a type of intramolecular nucleophilic aromatic substitution. Work has previously been completed by a member of the Greaney group to discover a set of optimised conditions for the rearrangement. Part one of this report investigated the scope of the rearrangement using the optimised reaction conditions. The set reaction conditions can be seen below. The sulfonamide first attacks the carbonyl of the acyl chloride, displacing a chloride ion to get the addition product. The CH2 next to the carbonyl group is then deprotonated by sodium hydroxide and subsequently attacks the carbon of the aromatic ring which is bonded to SO2. SO2 is then displaced and the negative charge is pushed onto the nitrogen. The nitrogen is then reprotonated to give the Smiles product. The second reaction investigates the Smiles Rearrangement utilising an ortho nitro group which interestingly yields an indazole, which can be seen below. Part two of this report investigated a potential novel Smiles Rearrangement, inspired by previous work completed by a member of the Greaney group that worked on aminoarylation of alkynes. Part three of this report investigated N-Heterocyclic Carbenes (NHCs) as organocatalysts in a bid to perform a potential novel electrophilic substitution of electron-deficient aromatic rings.

Date of Award	1 Aug 2019
Original language	English
Awarding Institution	The University of Manchester
Supervisor	David Procter (Supervisor) & Michael Greaney (Supervisor)