magistrsko delo
Povzetek
V sklopu magistrskega dela sem preučevala asimetrične pretvorbe derivatov pirolinona. Enantioselektivno sintezo sem dosegla z uporabo kiralnih nekovalentnih bifunkcionalnih organokatalizatorjev. Moje delo je obsegalo pripravo knjižnice racemnih produktov, s katerimi sem določila pogoje ločitve enantiomerov na kiralni HPLC koloni, ter enantiomerno obogatenih produktov, ki sem jim določila enantiomerni presežek. Sprva sem izvedla [4+2] anulacijo N-nesubstituiranih ariliden-Δ2-pirolin-4-onov z malononitrilom, rezultat katere so enantiomerno obogateni derivati dihidropirano[3,2-b]pirola. Pri določevanju enantiomernega presežka pretvorbe s kiralno HPLC kolono sem naletela na veliko dejavnikov, ki močno vplivajo na natančno določitev le-tega. V drugem delu sem kot izhodne substrate organokataliziranih pretvorb uporabila derivate tetramskih kislin. Z 1,4-adicijo tetramskih kislin na derivate trans-β-nitrostirena sem s tvorbo vezi C–C ustvarila kiralni center. Sintetizirala sem manjšo knjižnico aduktov tetramskih kislin in derivatov trans-β-nitrostirena, na katerih sem izvedla O-alkiliranje. Na izbrani neracemni N-Gly-Boc substituirani tetramski kislini sem izvedla serijo naknadnih pretvorb. S strategijo ortogonalne zaščite in peptidne kemije sem sintetizirala makrociklični produkt, ki vsebuje skelet pirolin-2-ona.
Ključne besede
organska sinteza;asimetrična sinteza;bifunkcionalna nekovalentna organokataliza;derivati pirolinonov;pirolinonski derivati;peptidna kemija;makrociklizacija;magistrska dela;
Podatki
Jezik: |
Slovenski jezik |
Leto izida: |
2021 |
Tipologija: |
2.09 - Magistrsko delo |
Organizacija: |
UL FKKT - Fakulteta za kemijo in kemijsko tehnologijo |
Založnik: |
[A. Gorenc] |
UDK: |
547.74(043.2) |
COBISS: |
86460675
|
Št. ogledov: |
386 |
Št. prenosov: |
115 |
Ocena: |
0 (0 glasov) |
Metapodatki: |
|
Ostali podatki
Sekundarni jezik: |
Angleški jezik |
Sekundarni naslov: |
Application of pyrrolone involving substrates in organocatalysed reactions |
Sekundarni povzetek: |
In this master’s thesis, the research was focused on the application of pyrrolinone derivatives in asymmetric transformations. Enantioselective synthesis was achieved with the application of chiral noncovalent bifunctional organocatalysts. This work covers the preparation of a library of racemic compounds, that were used for the optimization of chiral HPLC method for the separation of enantiomers and subsequently for the determination of enantiomeric excess of the corresponding enantiomerically enriched compounds. In the first part, [4+2] annulation of N-unsubstituted arylidene-Δ2-pyrrolin-4-ones with malononitrile were examined, which resulted in nonracemic dihydropyrano[3,2-b]pyrrole derivatives. The determination of enantiomeric excess of chiral nonracemic compounds, done by chiral HPLC method, was accompanied with numerous factors, that must be put into the consideration, to be able to obtain accurate enantioselectivity results. In the following research, tetramic acids derivatives were applied in organocatalyzed reactions. 1,4-addition of tetramic acids to trans-β-nitrostyrene derivatives resulted in a chiral center formation as new C–C bond was formed. A small library of O-alkylated adducts of tetramic acids and trans-β-nitrostyrene derivatives was synthesized. A chiral nonracemic N-Gly-Boc substituted tetramic acid derivative was used for the selected follow-up modifications. With the implementation of orthogonal protection and peptide chemistry, macrocyclic product containing pyrrolin-2-one heterocycle was synthesized. |
Sekundarne ključne besede: |
asymmetric synthesis;bifunctional noncovalent organocatalysis;pyrrolinone derivatives;peptide chemistry;macrocyclization; |
Vrsta dela (COBISS): |
Magistrsko delo/naloga |
Študijski program: |
1000375 |
Konec prepovedi (OpenAIRE): |
1970-01-01 |
Komentar na gradivo: |
Univ. v Ljubljani, Fak. za kemijo in kemijsko tehnologijo, smer Kemija |
Strani: |
101 str. |
ID: |
13534229 |