Enantioselective synthesis of novel N-C atropisomers, their properties and potential applications

Abstract

The principal aim of this project was the development of new catalytic methods to control asymmetry in the formation of N-C biaryl atropisomers. Initial efforts were directed towards the synthesis of enantioenriched 4-quinolinones with subsequent organometallic addition yielding quinolinium salts with varying degrees of enantioselectivity retention. Discussion of the synthesis, chemical properties and structural characterisation of the novel class of axially chiral quinolinium salts thus prepared is included.

General understanding of the asymmetric Buchwald-Hartwig coupling used to generate atropselectivity in 4-quinolinones was furthered by the research undertaken, and subsequent efforts to improve upon the enantioselectivity achieved in that step were directed towards an atropselective DKR of 2 pyridones. During this work, N-aryl pyridones were synthesized in good yields and with good enantioselectivity via asymmetric phase-transfer catalysis.

In both chapters of this thesis, published and unpublished work relating to the optimization of key atropselective steps in the synthesis of N-C atropisomers is described in detail. Additional description of DFT studies, as utilized to supplement fundamental understanding of the chemistry, are also included and discussed in conjunction with experimental results.

Date of Award	Jul 2022
Original language	English
Awarding Institution	Queen's University Belfast
Sponsors	Northern Ireland Department for the Economy
Supervisor	Peter Knipe (Supervisor) & Paul Dingwall (Supervisor)