Driver, Ross B.
(2017)
i) Design and Synthesis of Butadiene Substrates for
Organocatalytic Transformations ii) Synthesis of
Functionalized Biaryls and Pyran Derivatives.
PhD thesis, National University of Ireland Maynooth.
Abstract
This thesis details the exploration of a number of discrete but interlinked projects. 1) The
synthesis of 1,3-bis-subsitituted electron-deficient butadiene substrates for the study of
vinylogous Michael-type addition chemistry through organocatalytic means. The synthesis
of these electron-deficient butadienic systems proved to be quite challenging and required
extensive reaction screening in order to access these substrates in synthetically useful scales.
A modular approach to diene synthesis was developed in order to gain access to distinct
butadiene families through the combination of aryl formyl acrylonitriles and stabilized ylides
in a base-free Wittig olefination reaction. The use of the polymerization inhibitor 8
hydroxyquinoline was found to be key to the synthesis of these challenging substrates to
prevent the vinyl nitriles from polymerizing. Density Functional Theory (DFT) calculations
were also performed on the butadiene substrates in order to develop a better understanding
of the conformations and geometries the butadienes adopt, a key part of their potential
reactivity. 2) The study of these newly synthesized butadienes in an asymmetric
organocatalytic 1,6-conjugate addition/cyclization to yield enantioenriched cyclic
hexadienes did not yield the expected products and instead yielded densely functionalized
biaryl species which are of some synthetic interest. Our attentions were then turned to the
directed synthesis of these biaryls. This was accomplished through the use of stoichiometric
quantities of piperidine in order to reduce the potential for polymerization or side-reactions
which would consume the starting material. A study into the aromatization of the cyclic
hexadienes into the biaryl species was also carried out. A crystal structure of one of the biaryl
species 125 was also elucidated which unambiguously confirmed the structure of the biaryls.
3) A key synthetic intermediate in the synthesis of the 1,3-bis-subsitituted butadienes was
the aryl formyl acrylonitriles. This class of compounds has been little studied and a number
of interesting reactivities that they exhibit were discovered during the attempted syntheses
of butadienes. The final part of this thesis details the synthesis of 2-amino-4H-pyrans from
the conjugate addition of malononitrile to aryl formyl acrylonitriles and the synthesis of 3,4
dihydro-2H-pyrans through Inverse Electron Demand Hetero-Diels-Alder (IEDHDA)
cycloaddition reactions. An asymmetric variant of the synthesis of 2-amino-4H-pyrans was
attempted. In depth discussion on the regio- and stereoselectivity of the IEDHDA is also given
and supported by detailed NMR analysis.
| Item Type: |
Thesis
(PhD)
|
| Keywords: |
Design; Synthesis; Butadiene Substrates;
Organocatalytic Transformations; Functionalized Biaryls; Pyran Derivatives; |
| Academic Unit: |
Faculty of Science and Engineering > Chemistry |
| Item ID: |
13841 |
| Depositing User: |
IR eTheses
|
| Date Deposited: |
15 Jan 2021 12:43 |
| URI: |
|
| Use Licence: |
This item is available under a Creative Commons Attribution Non Commercial Share Alike Licence (CC BY-NC-SA). Details of this licence are available
here |
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