Εξειδίκευση τύπου :	Άρθρο σε επιστημονικό περιοδικό
Τίτλος:	Intramolecular cyclization of β-nitroso-o-quinone methides. A theoretical endoscopy of a potentially useful innate 'reclusive' reaction
Δημιουργός/Συγγραφέας:	[EL] Τζέλη, Δήμητρα[EN] Tzeli, Demeter Tsoungas P.G. [EL] Πετσαλάκης, Ιωάννης Δ.[EN] Petsalakis, Ioannis D. Kozielewicz P. Zloh M.
Εκδότης:	Elsevier
Ημερομηνία:	2015
Γλώσσα:	Αγγλικά
ISSN:	0040-4020
DOI:	10.1016/j.tet.2014.11.020
Περίληψη:	Oxidatively generated β-nitroso-o-quinone methides undergo an o- and/or peri-intramolecular cyclization to arene-fused 1,2-oxazoles, 1,2-oxazines or indoles. The reaction, found to be an innate process, has been scrutinized by DFT/B3LYP and MP2 calculations. Due to its rapidity, the process has been termed a 'reclusive' one. Competing o-(1,5)- and peri-(1,6)- or (1,5)-cyclizations advance via successive transition states. Activation barriers are drastically lowered in AcOH, probably through H hopping or tunnelling whereas they are barely reduced in other solvents. Aromaticity indices, such as HOMA, IA and ABO, have been used to assess the stability of the end-heterocycles and the preponderance of any one of them. Thus, the preferred cyclization mode, that is, the prevalence or exclusive formation of one of the heterocycles, appears to be oxidant-directed rather than determined by the quinone methide geometry. The question of the peri-cyclization, being a primary or a secondary process, has been tackled.
Τίτλος πηγής δημοσίευσης:	Tetrahedron
Τόμος/Κεφάλαιο:	71
Τεύχος:	2
Σελίδες:	359-369
Θεματική Κατηγορία:	[EL] Φυσική και θεωρητική χημεία[EN] Physical and theoretical chemistry
Λέξεις-Κλειδιά:	DFT and MP2 calculations Innate reclusive reaction Intramolecular o- and peri-cyclization β-Nitroso-o-quinone methides
Αξιολόγηση από ομότιμους (peer reviewed):	Ναι
Κάτοχος πνευματικών δικαιωμάτων:	© 2014 Elsevier Ltd. All rights reserved.
Όροι και προϋποθέσεις δικαιωμάτων:	All Open Access, Green
Εμφανίζεται στις συλλογές:	Ινστιτούτο Θεωρητικής και Φυσικής Χημείας (ΙΘΦΧ) - Επιστημονικό έργο