Unit:
Κατεύθυνση Οργανική Σύνθεση και Εφαρμογές της στη Χημική ΒιομηχανίαLibrary of the School of Science
Supervisors info:
Γεώργιος Χ. Βουγιουκαλάκης, Αναπληρωτής Καθηγητής, Τμήμα Χημείας, ΕΚΠΑ
Γκιμήσης Αθανάσιος, Καθηγητής, Τμήμα Χημείας, ΕΚΠΑ
Τσουρέας Νικόλαος, Επίκουρος Καθηγητής, Τμήμα Χημείας, ΕΚΠΑ
Original Title:
Ανάπτυξη καταλυτικών πρωτοκόλλων νικελίου και χαλκού για την οξείδωση ή/και ισομερείωση (ομοαλλυλικών) αλκοολών
Translated title:
Developement of nickel and copper catalytic protocols for the oxidation or/and isomerization of (homoallylic) alcohols
Summary:
The oxidation of alcohols to carbonyl compounds is one of the most significant
reactions in Organic Chemistry. Due to their pivotal role in industrial and
academic fields, these reactions attract a great attention, leading to new
catalysts, substrates, oxidants, and applications. As far as the oxidants are
concerned, stoichiometric oxidations with transition metal compounds are still
in common use, despite the formation of a large amount of undesirable products
and organic solvents. The most used oxidants (such as PCC and Jones
reagent) are mutagenic, toxic, and dangerous for the environment. From an
environmental point of view, the development of methods which use transition
metal catalysts and minimize the amount and toxicity of the released waste, is
strongly encouraged. In this respect, the recovery and reuse of the catalyst is
a further important goal. The present work describes the development of two
independent, innovative catalytic protocols for the oxidation of alcohols with
nickel and copper catalysts, aiming to viable and sustainable catalysis.
The thesis begins with the development of a nickel-based catalytic system.
According to this approach, with the same nickel (I) complex the oxidation of
the homoallyl alcohol and the isomerization of the double bond to form the
desired ketones are carried out in one pot and in one step. This catalytic
approach is innovative and particularly beneficial to the industry in terms of
saving time and resources. The first results obtained from this catalytic system
are promising for further study.
The second part of the thesis deals with the development of a new copperbased protocol. The study begins with the synthesis of a library of nonsymmetrical and symmetrical perfluorinated copper(I) complexes bearing Nheterocyclic carbenes. The use of the in situ formed catalytic system from a
copper source (Cu2O) and a perfluorinated N-heterocyclic carbene salt
precursor in the aerobic oxidation of alcohols follows. The reaction uses
TEMPO as a co-catalyst and takes place at the interface of a biphasic solvent
system. The desired carbonyl compound and starting material is in the organic
solvent and the perfluorinated catalyst remains in the perfluorinated phase. In
this way, the purification and isolation of the product is facile. The protocol
works well at low catalytic loading and the catalyst can be reused six times
without significant decrease in efficiency. Thus, the recycling of the catalyst
solution is achieved, which would potentially be useful in industry.
Main subject category:
Science
Keywords:
Sustainable catalysis, nickel (I) complex, perfluorinated copper (I) complex, N-heterocyclic carbenes, recyclability of catalyst
File:
File access is restricted until 2028-03-16.
MSc Drymona Maria.pdf
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File access is restricted until 2028-03-16.
