Edinburgh Research Archive >
Chemistry, School of >
Chemistry thesis and dissertation collection >
Please use this identifier to cite or link to this item:
|Title: ||Novel benzyne insertion reactions & medium-ring synthesis by oxidative C-H coupling|
|Authors: ||Pintori, Didier Gil|
|Supervisor(s): ||Greaney, Michael F.|
|Issue Date: ||23-Nov-2011|
|Publisher: ||The University of Edinburgh|
|Abstract: ||This thesis is divided into two main chapters, which are focused on two separated
and uncorrelated research areas. The first part of this thesis is dedicated to the
research I carried out in benzyne chemistry and the second part is focused on
catalytic C-H bond activation.
In the first place, a novel insertion reaction of arynes into the nitrogen-carbonyl σ-bond of amides has been investigated as a rapid and powerful approach for the
preparation of valuable ortho-disubstituted arenes. Readily available aromatic amides
undergo smooth insertion when treated with O-triflatophenyl silane aryne precursors,
producing versatile anthranilic derivatives in good to excellent yields. The process is
entirely metal-free and has been expanded to the synthesis of biologically active
heterocycles such as acridones and acridines.
Secondly, the synthesis of medium-sized ring systems by intramolecular oxidative CH
bond coupling has been explored.
Despite the abundance of biologically active natural products featuring mediumsized
rings, the synthesis of such ring systems using classical synthetic routes faces
many challenges and has led to a dearth of medium ring compounds in medicinal
chemistry. In contrast to the more facile 5-membered ring synthesis by oxidative C-H
coupling, medium ring synthesis has not been previously reported using this
approach. The chemistry, which requires zero pre-functionalisation of the substrates,
is catalysed by palladium and has been exemplified using heteroaromatic substrates
at the core of numerous biologically active molecules. The mechanism of the
reaction has also been studied and a catalytic cycle has been proposed.|
Engineering and Physical Sciences Research Council (EPSRC)
|Appears in Collections:||Chemistry thesis and dissertation collection|
Items in ERA are protected by copyright, with all rights reserved, unless otherwise indicated.