Opis

• Tytuł:
  A photo-Smiles rearrangement: Mechanistic investigation of the formation of Blatter radical helicenes
• Twórca:
  Kaszynski, Piotr
• Współtwórca:
  piotr.kaszynski@chemia.uni.lodz.pl;
  Kaszynski, Piotr
• Opis:
  Photocyclization of 8-aryloxy-3-phenylbenzo[e]- [1,2,4]triazines leads to helicene radicals. Structural analysis of radicals leuco forms by two-dimensional correlation nuclear magnetic resonance methods demonstrated that the photo- cyclization involves a Smiles rearrangement and exclusive formation of a single rearranged product for all substrates. Density functional theory investigations indicate that the mechanism requires the T1 state with (n, π*) character localized on the benzo[e][1,2,4]triazine (BT) fragment and at least one occupied π molecular orbital (MO) localized on the aryloxy fragment with an energy that is higher than that of the n MO. This electronic structure is favorable for aryl-to-BT single-electron transfer and formation of a zwitterion, which undergoes an intramolecular polar cyclization followed by ring opening of the resulting spirooxazole. The proposed mechanism represents a new variation of photo-Smiles rearrangement and appears to be general for the photochemical formation of planar Blatter radicals.;
  Support for this project has been provided by National Science Center Grant 2020/38/A/ST4/00597.
• Dostępność obiektu:
  Dostęp otwarty
• Prawa:
  ACS;
  Uznanie autorstwa 4.0 Międzynarodowe;
  http://creativecommons.org/licenses/by/4.0
• Data:
  2025.03.10;
  2025.01.10
• Typ:
  Article
• Język:
  angielski
• Format:
  application/pdf
• Wydawca:
  ACS
• Relacja:
  The Journal of Organic Chemistry;;
  90
• Temat i słowa kluczowe:
  Organic chemistry;
  synthesis;
  mechanism
• Identyfikator:
  0022-3263;
  http://hdl.handle.net/11089/54937 ;
  1520-6904;
  10.1039/JR9310003264
• Dostawca danych:
  Repozytorium Uniwersytetu Łódzkiego
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