We found a match
Your institution may have access to this item. Find your institution then sign in to continue.
- Title
Synchronous and Zwitterionic Channels of the Reaction of (R)-5-Methyl-2-(propan-2-ylidene)cyclohexanone with 4-Phenyl-3H-1,2,4-triazole-3,5(4H)-dione.
- Authors
Bodrikov, I. V.; Kurskii, Yu. A.; Chiyanov, A. A.; Subbotin, A. Yu.; Kuropatov, V. A.
- Abstract
The reaction of pulegone with 4-phenyl-3H-1,2,4-triazole-3,5(4H)-dione as enophile gives two known epimers, 1-[(1R,4R)-4-methyl-2-oxo-1-(prop-1-en-2-yl)cyclohexyl]-4-phenyl-1,2,4-triazolidine-3,5-dione (RR isomer) and 1-[(1S,4R)-4-methyl-2-oxo-1-(prop-1-en-2-yl)cyclohexyl]-4-phenyl-1,2,4-triazolidine-3,5-dione (SR isomer). In addition, we isolated previously unknown 1-{2-[(4R)-4-methyl-6-oxocyclohex-1-en-1-yl]propan-2-yl}-4-phenyl-1,2,4-triazolidine-3,5-dione. According to the results of quantum chemical simulation, the isomeric products of hydrogen substitution in pulegone by the enophile are formed along three pathways. The SR isomer is formed via a concerted ene reaction. The other two channels involve approach of the enophile from the R side of pulegone and include two consecutive steps. The first step generates intermediate unsymmetrical cyclic aziridine cation, and elimination of proton from one of the geminal methyl groups of that intermediate yields the RR isomer with a terminal double bond. Proton elimination from methylene group of the pulegone fragment gives a cyclic compound with internal double bond. The ratio of the isomer with internal double bond and the RR isomer depends on the polarity of aprotic solvent.
- Subjects
ENE reactions; CYCLOHEXANONES; DOUBLE bonds; APROTIC solvents; CYCLIC compounds; AZIRIDINATION; ZWITTERIONS
- Publication
Russian Journal of Organic Chemistry, 2023, Vol 59, Issue 12, p2124
- ISSN
1070-4280
- Publication type
Article
- DOI
10.1134/S1070428023120096