Organocatalysis by halogen bonding donors: A promising complement to hydrogen bond-based catalysis.
Citation:
Garcia, Marianne Rica, Organocatalysis by halogen bonding donors: A promising complement to hydrogen bond-based catalysis., Trinity College Dublin, School of Chemistry, Chemistry, 2023Download Item:
Abstract:
Catalytic transformations, previously dominated by metal catalysts, have seen
exponential growth in the use of organocatalysts over the last two decades. The
emergence of small organic molecules employed to facilitate chemical reactions has
played a significant role in a more economical and sustainable synthetic approach.
Examples of such molecules include the well-established hydrogen bond catalysts
and their analogous halogen bond catalysts. While halogen bond catalysts are
known to have more desirable features than their predecessor, such as a higher
degree of directionality and tunability, there have only been a handful of reports
on the use of halogen bond-based catalysts in organocatalysis.
Herein, in this project, theoretical investigations have been carried out in rela-
tion to non-covalent interactions within organocatalysis. The first study involved
hydrogen bond interactions to analyse the type of binding modes that can simul-
taneously form and the influences cooperativity and secondary interactions have
on them.
In the second part of this research project, halogen bond-based catalysis was
studied and for that two different reactions were theoretically investigated. The
first reaction involved a halide abstraction reaction between a benzyl bromide
and acetonitrile, catalysed by two catalysts to reveal the reaction mechanism and
to determine the binding modes of each catalyst. The second reaction carried out
was a Michael addition reaction between a trans-crotonophenone and an indole,
catalysed by five different catalysts, in order to establish the effects produced
when different halogen atoms are used and to study the substituent effects on the
halogen bond strength by modifying the catalytic scaffolds. A successful redesign
of two new catalysts was established based on the results obtained.
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https://tcdlocalportal.tcd.ie/pls/EnterApex/f?p=800:71:0::::P71_USERNAME:GARCIAM1Description:
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Author: Garcia, Marianne Rica
Advisor:
Trujillo, CristinaPublisher:
Trinity College Dublin. School of Chemistry. Discipline of ChemistryType of material:
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