Oxidopyridinium Cycloadditions Revisited: A Combined Computational and Experimental Study on the Reactivity of 1-(2-Pyrimidyl)-3-oxidopyridinium Betaine.
J Org Chem
; 88(5): 3193-3207, 2023 Mar 03.
Article
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| MEDLINE
| ID: mdl-36802575
ABSTRACT
To investigate the effect of N-substituents on their reactivity and selectivity of oxidopyridinium betaines, we performed density functional theory (DFT) calculations of model cycloadditions with N-methylmaleimide and acenaphthylene. The theoretically expected results were compared with the experimental results. Subsequently, we demonstrated that 1-(2-pyrimidyl)-3-oxidopyridinium can be used for (5 + 2) cycloadditions with various electron-deficient alkenes, dimethyl acetylenedicarboxylate, acenaphthylene, and styrene. In addition, a DFT analysis of the cycloaddition of 1-(2-pyrimidyl)-3-oxidopyridinium with 6,6-dimethylpentafulvene suggested the possibility of pathway bifurcations involving a (5 + 4)/(5 + 6) ambimodal transition state, although only (5 + 6) cycloadducts were experimentally observed. A related (5 + 4) cycloaddition was observed in the reaction of 1-(2-pyrimidyl)-3-oxidopyridinium with 2,3-dimethylbut-1,3-diene.
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Base de dados:
MEDLINE
Idioma:
En
Revista:
J Org Chem
Ano de publicação:
2023
Tipo de documento:
Article
País de afiliação:
Japão