title: Experimental and Theoretical Study of an Intramolecular CF3-Group Shift in the Reactions of α-Bromoenones with 1,2-Diamines.
abstract: The reactions of trifluoromethylated 2-bromoenones and N,N'-dialkyl-1,2-diamines have been studied. Depending on the structures of the starting compounds, the formation of 2-trifluoroacetylpiperazine or 3-trifluoromethylpiperazine-2-ones was observed. The mechanism of the reaction is discussed in terms of multistep processes involving sequential substitution of bromine in the starting α-bromoenones and intramolecular cyclization of the captodative aminoenones as key intermediates to form the target heterocycles. The results of theoretical calculations are in perfect agreement with the experimental data. The unique role of the trifluoromethyl group in this reaction is demonstrated.
authors.affiliation: Department of Chemistry, Moscow State University, Leninskie Gory, Moscow 119992 (Russia), Fax: (+7) 495-932-8846.
authors.forename: Vasily M
authors.initials: VM
authors.lastname: Muzalevskiy
authors.affiliation: Department of Chemistry, Moscow State University, Leninskie Gory, Moscow 119992 (Russia), Fax: (+7) 495-932-8846.
authors.forename: Yury A
authors.initials: YA
authors.lastname: Ustynyuk
authors.affiliation: Department of Chemistry, Moscow State University, Leninskie Gory, Moscow 119992 (Russia), Fax: (+7) 495-932-8846.
authors.forename: Igor P
authors.initials: IP
authors.lastname: Gloriozov
authors.affiliation: Department of Chemistry, Moscow State University, Leninskie Gory, Moscow 119992 (Russia), Fax: (+7) 495-932-8846.
authors.forename: Vyacheslav A
authors.initials: VA
authors.lastname: Chertkov
authors.affiliation: A. E. Favorsky Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1, Favorsky Str., Irkutsk 664033 (Russia), Fax: (+7) 3952-419346. rulev@irioch.irk.ru.
authors.forename: Alexander Yu
authors.initials: AY
authors.lastname: Rulev
authors.affiliation: A. E. Favorsky Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1, Favorsky Str., Irkutsk 664033 (Russia), Fax: (+7) 3952-419346.
authors.forename: Evgeniy V
authors.initials: EV
authors.lastname: Kondrashov
authors.affiliation: A. E. Favorsky Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1, Favorsky Str., Irkutsk 664033 (Russia), Fax: (+7) 3952-419346.
authors.forename: Igor A
authors.initials: IA
authors.lastname: Ushakov
authors.affiliation: A. E. Favorsky Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1, Favorsky Str., Irkutsk 664033 (Russia), Fax: (+7) 3952-419346.
authors.forename: Alexey R
authors.initials: AR
authors.lastname: Romanov
authors.affiliation: Department of Chemistry, Moscow State University, Leninskie Gory, Moscow 119992 (Russia), Fax: (+7) 495-932-8846. nen@acylium.chem.msu.ru.
authors.forename: Valentine G
authors.initials: VG
authors.lastname: Nenajdenko
keywords: fluorine; heterocycles; reaction mechanisms; rearrangement; substituent effects