Naslov
Bergman cyclization of acyclic amino acid-derived enediynes leads to the formation of 2, 3-dihydro-benzo[f]isoindoles

Autori
Gredičak, Matija ; Matanović, Ivana ; Zimmermann, Boris ; Jerić, Ivanka

Izvornik
Journal of organic chemistry (0022-3263) 75 (2010); 6219-6228

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
Bergman cyclization; enediynes; amino acids

Sažetak
Enediyne-peptide conjugates are recently recognized as useful tools in targeting various proteins, while mechanism underlying observed activity remains somewhat unclear. Addressing these issues, we have prepared acyclic amino acid-derived enediynes and disclosed a novel thermally induced cyclization-elimination pathway. Initial formation of 1, 4-benzene diradical and H-atom abstraction from external donor is followed by SN2 substitution leading to 2, 3-dihydro-benzo[f]isoindoles. Proposed mechanism is supported by experimental and computational data. Additionally, we showed that amino acid side-chains, although placed three bonds away from acetylene terminuses, have an appreciable influence on the reactivity of studied enediynes. These results demonstrate that amino acid or peptide parts of enediyne-peptide conjugates cannot be considered as recognition elements exclusively, but may also participate in various reactions through amine functionality.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

POVEZANOST RADA