Εξειδίκευση τύπου :	Άρθρο σε επιστημονικό περιοδικό
Τίτλος:	Self Cycloaddition of o-Naphthoquinone Nitrosomethide to (±) Spiro{naphthalene(naphthopyranofurazan)}-one Oxide: An Insight into its Formation
Δημιουργός/Συγγραφέας:	[EL] Τζέλη, Δήμητρα[EN] Tzeli, Demeter Gerontitis, Ioannis E [EL] Πετσαλάκης, Ιωάννης Δ.[EN] Petsalakis, Ioannis D. Tsoungas, Petros G. Varvounis, George
Ημερομηνία:	2022-11-23
Γλώσσα:	Αγγλικά
ISSN:	2192-6506 2192-6506
DOI:	10.1002/cplu.202200313
Άλλο:	36479609
Περίληψη:	2-Hydroxy-1-naphthaldehyde oxime was oxidized by AgO (or Ag2 O), in presence of N-methyl morpholine N-oxide (NMMO), to the title spiro adduct-dimer (±)-Spiro{naphthalene-1(2H),4'-(naphtho[2',1':2,3]pyrano[4,5-c]furazan)}-2-one-11'-oxide by a Diels-Alder(D-A) type self-cycloaddition, through the agency of an o-naphthoquinone nitrosomethide (o-NQM). Moreover, 2-hydroxy-8-methoxy-1-naphthaldehyde oxime was prepared and subjected to the same oxidation conditions. Its sterically guided result, 9-methoxynaphtho[1,2-d]isoxazole, was isolated, instead of the expected spiro adduct. The peri intramolecular H bonding in the oxime is considered to have a key contribution to the outcome. Geometry and energy features of the oxidant- and stereo-guided selectivity of both oxidation outcomes have been explored by DFT, perturbation theory and coupled cluster calculations. The reaction free energy of the D-A intermolecular cycloaddition is calculated at -82.0 kcal/mol, indicating its predominance over the intramolecular cyclization of ca. -37.6 kcal/mol. The cycloaddition is facilitated by NMMO through dipolar interactions and hydrogen bonding with both metal complexes and o-NQM. The 8(peri)-OMe substitution of the reactant oxime sterically impedes formation of the spiro adduct, instead it undergoes a more facile cyclodehydration to the isoxazole structure by ca. 4.9 kcal/mol.
Τίτλος πηγής δημοσίευσης:	ChemPlusChem
Τόμος/Κεφάλαιο:	87
Τεύχος:	12
Θεματική Κατηγορία:	[EL] Φυσική και θεωρητική χημεία[EN] Physical and theoretical chemistry
Λέξεις-Κλειδιά:	DFT calculations cycloaddition oxidation oximes spiro naphthoquinone
Κάτοχος πνευματικών δικαιωμάτων:	© 2022 The Authors. ChemPlusChem published by Wiley-VCH GmbH
Όροι και προϋποθέσεις δικαιωμάτων:	This is an open access article under the terms of the Creative Commons Attribution-NonCommercial-NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.
Ηλεκτρονική διεύθυνση στον εκδότη (link):	https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cplu.202200313
Σημειώσεις:	Supporting information supplied by the authors is available here: https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cplu.202200313
Εμφανίζεται στις συλλογές:	Ινστιτούτο Θεωρητικής και Φυσικής Χημείας (ΙΘΦΧ) - Επιστημονικό έργο