Graduate theses
Current Record: 30 of 246
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Title |
Α) Σύνθεση α,α-διχλωρο-β-κέτο εστέρων και μελέτη ενζυμικής αναγωγής τους Β) Σύνθεση και φωτοοξείδωση φαίνυλοκυκλοπεντενίου |
Alternative Title |
Α) Synthesis and enzymatic reduction of α,α-dichloro-β-keto esters Β) Synthesis and photooxidation of phenylcyclopente |
Author
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Κεφαλογιάννη, Μαρία
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Thesis advisor
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Σμόνου, Ιουλία
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Abstract |
The subject of the present thesis was the enantioselectivity study of the enzymatic
reduction of α,α-dichloro-β-keto esters with ketoreductases in order to form
compounds of high added value which can be used as intermediates in natural products
synthesis. The photooxidation of an alkene substrate was also studied using singlet
oxygen, 1Ο2, as well as the photooxidation test of the produced allylic alcohol through
an anthraquinone derivative in order to develop a synthetic route that combines
Biocatalysis and Photocatalysis.
In the first part, the enantioselective reduction of α,α-dichloro-β-keto esters using the
NADPH-dependent ketoreductase, KRED 101, to form the corresponding α,α-dichloroβ-hydroxy esters is presented. More specifically, 2,2-dichloro-3-cyclohexyl-3-
oxopropanoate methyl ester was synthesized as the substrate, its enzymatic reduction
was studied and the absolute configuration of the reduced product was determined using
MPA-esters. The reduction product, methyl 2,2-dichloro-3-cyclohexyl-3-hydroxypropanoate, was formed in excellent enantiomeric excess >99 % ee and in fairly good
yield. The enantioselective reduction of α,α-dichloro-β-keto ester substrates was then
studied in a four times larger scale and the reduction products were formed with
excellent enantioselectivity, in very good yields and.
In the second part, the synthesis of phenyl-cyclopentene and the study of its
photooxidation using singlet oxygen, 1Ο2 is presented. The photooxidation of the allylic
alcohol, 2-phenylcyclopent-2-en-1-ol, to form the corresponding enone was also
studied using the commercially available water-soluble sodium anthraquinone
sulfonate (SAS). The results of this specific photooxidation were not satisfactory.
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Language |
Greek |
Subject |
Anthraquinone |
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Enantioselective bioreduction |
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Ketoreductases |
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a,a-dichloro-b-keto esters |
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Ανθρακινόνη |
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Εναντιοεκλεκτική βιοαναγωγή |
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Κετορεδουκτάσες |
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Μοριακό οξυγόνο απλής κατάστασης |
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α-διχλωρο-β-κέτο εστέρες |
Issue date |
2022-11-24 |
Collection
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School/Department--School of Sciences and Engineering--Department of Chemistry--Graduate theses
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Type of Work--Graduate theses
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Permanent Link |
https://elocus.lib.uoc.gr//dlib/b/8/3/metadata-dlib-1666883740-930126-673.tkl
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Views |
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