Towards α-functionalization of aldehydes with unactivated electrophiles and catalytic enantioselective intramolecular [4+2] annulation of dienes and terminal alkynes
File(s)
Author(s)
Adeleke, Adekunle
Type
Thesis
Abstract
The union of organocatalysis with transition metal chemistry offers a myriad of novel methodologies for exploring chemical space. The versatility of enamine catalysis combined with Group 10 transition metal catalysis will therefore present unique opportunities for discovering hitherto unknown enantioselective transformations. The work described herein presents investigations into syntheses of chiral secondary amine bases and reaction screening towards achieving α-functionalisation of aldehyde compounds. Our effort towards realizing α-alkylation of aldehydes was unsuccessful. Subsequent exploration of α-arylation of aldehydes with pre–formed imine was moderately successful. In part 2, enantioselective intramolecular copper catalyzed cycloaddition of diene and alkynes was achieved. A cheap Cu(I) source, copper iodide was used as the metal catalyst, and a readily synthetically accessible chiral PyBox was used as a chiral ligand. The reactions occur in excellent yields and high enantioselectivities. The reactions are robust; they tolerate the presence of water and air.
Version
Open Access
Date Issued
2023-11
Date Awarded
2024-04
Copyright Statement
Creative Commons Attribution NonCommercial Licence
License URL
Advisor
Cordier, Christopher
Spivey, Alan
Publisher Department
Chemistry
Publisher Institution
Imperial College London
Qualification Level
Doctoral
Qualification Name
Doctor of Philosophy (PhD)