Naslov
Stereoselectivity in Phthalimide Initiated Photocyclization of Peptides

Autori
Sohora, Margareta ; Sović, Irena ; Mlinarić-Majerski, Kata ; Basarić, Nikola

Vrsta, podvrsta i kategorija rada
Sažeci sa skupova, sažetak, znanstveni

Izvornik
25. Hrvatski skup kemičara i kemijskih inženjera s međunarodnim sudjelovanjem ; 3. simpozij Vladimir Prelog : knjiga sažetaka = 25th Croatian Meeting of Chemist and Chemical Engineers with international participation. 3rd symposium “Vladimir Prelog” : Book of Abstracts / Šantić, Ana ; Đaković, Marijana - Zagreb : Hrvatsko društvo kemijskih inženjera i tehnologa (HDKI) ; Hrvatsko kemijsko drustvo, 2017, 65-65

ISBN
978-953-552327-7

Skup
25. Hrvatski skup kemičara i kemijskih inženjera s međunarodnim sudjelovanjem ; 3. simpozij Vladimir Prelog = 25th Croatian Meeting of Chemist and Chemical Engineers with international participation. 3rd symposium “Vladimir Prelog”

Mjesto i datum
Poreč, Hrvatska, 19.04.2017. - 22.04.2017

Vrsta sudjelovanja
Predavanje

Vrsta recenzije
Međunarodna recenzija

Ključne riječi
peptides ; phthalimide ; photochemistry ; stereoselectivity

Sažetak
Phthalimide in the triplet excited state is a good oxidizing agent. Therefore, upon photoexcitation of the phthalimide to the triplet state, alkyl-carboxylates are easily oxidized by inter- or intramolecular single electron transfer (SET) from the carboxylate to the phthalimide [1]. The SET promotes irreversible decarboxylation leading to radical intermediates, which was implemented in different synthetic applications. For example, such a decarboxylation has been used in the photocyclization of crown ethers or peptides [1, 2]. We have become interested in photoinduced decarboxylation reactions of different phthalimide derivatives of adamantane aminoacids [3, 4]. Within the scope of that research, we have found an example of highly enantioselective dipeptide cyclization with a memory of chirality [5]. In the continuation of the research we investigated photocyclization of tetra- and pentapeptides 1-6 (Scheme 1). The photocyclizations of 1-6 to peptides 7-12 proceed in moderate yields, but with high diastereoselectivity. Interestingly, preliminary results indicate different stereochemistry in the cyclic products in tetra- and pentapeptides and suggest that the chiral information in the peptide chains leads to a complete inversion or retention of configuration.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

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