Study of the Features of the Reaction of Arylcyclopropanes with Nitrozonium Ethyl Sulfate or Nitrozonium Tetrafluoroborate

• Published in: Russian journal of organic chemistry Vol. 56; no. 5; pp. 753 - 762
• Main Authors: Gavrilova, A. Yu, Bondarenko, O. B., Tikhanushkina, V. N., Solodovnikova, T. A., Zyk, N. V.
• Format: Journal Article
• Language: English
• Published: Moscow Pleiades Publishing 01.05.2020; Springer Nature; Springer Nature B.V
• Subjects: Aromatic compounds; Chemistry; Chemistry and Materials Science; Chemistry, Organic; Cyclopropane; Organic Chemistry; Physical Sciences; Regioselectivity; Science & Technology; Sulfur; Sulfur trioxide; Sulfuric acid; regioselectivity; arylcyclopropane; nitrosation; isoxazoline; nitrosonium tetrafluoroborate; skeletal rearrangements; alkyl nitrite; CYCLOPROPANE RING; ROUTE; INSERTION; KETONES; 4,5-DIHYDROISOXAZOLES; PHENYLCYCLOPROPANES
• ISSN: 1070-4280; 1608-3393
• DOI: 10.1134/S107042802005005X

The reactions of diaryl-, aryl-, and alkyl–arylcyclopropanes with ethyl nitrite in the presence of sulfur trioxide and sulfur trioxide dioxane complex, as well as the reactions of 1-alkyl-2-arylcyclopropanes with NOBF 4 were studied. It was found that the attack of the nitrosonium cation, accompanied by the formation of a benzyl carbocation, leads to the formation of isoxazolines. The introduction of bulky alkyl substituents into the cyclopropane ring changes the regioselectivity of nitrosation, favoring the attack of the electrophilic particle on the benzyl position and leading to the competitive formation of an alkyl carbocation. Depending on the structure of the alkyl substituent, both products of intramolecular heterocyclization accompanied by skeletal rearrangements and products formed with the participation of an external nucleophile are formed.