Unexpected Ring Opening During the Imination of Camphor-Type Bicyclic Ketones

Unexpected Ring Opening During the Imination of Camphor-Type Bicyclic Ketones Full article

Journal

European Journal of Organic Chemistry
ISSN: 1434-193X , E-ISSN: 1099-0690

Output data

Year: 2021, Volume: 2021, Number: 3, Pages: 452-463 Pages count : 12 DOI: 10.1002/ejoc.202001397

Tags

(−)-Fenchone; Benzimidazoles; Camphor; Monoterpenoids; Single-stage synthesis

Authors

Chernyshov Vladimir V. ^1,2 , Yarovaya Olga I. ^1,2 , Vatsadze Sergey Z. ⁴ , Borisevich Sophia S. ⁵ , Trukhan Sergey N. ^2,3 , Gatilov Yuri V. ^1,2 , Peshkov Roman Yu. ² , Eltsov Ilia V. ² , Martyanov Oleg N. ^2,3 , Salakhutdinov Nariman F. ^1,2

Affiliations

1	N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS, 9 Acad. Lavrentiev Ave., Novosibirsk, 630090, Russian Federation
2	Novosibirsk State University, Pirogova St. 1, Novosibirsk, 630090, Russian Federation
3	Boreskov Institute of Catalysis SB RAS, 5 Acad. Lavrentiev Ave., Novosibirsk, 630090, Russian Federation
4	N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninski pr., 47, Moscow, 119991, Russian Federation
5	Laboratory of Chemical Physics, Ufa Institute of Chemistry, Ufa Federal Research Center, Russian Academy of Sciences, 71 Octyabrya pr., Ufa, 450054, Russian Federation

A new ring opening reaction was found while attempting to isolate the imines from ortho-heteroatom substituted anilines and camphor-like bicyclic ketones. The benzoazoles containing a cyclopentanemethyl group at position 2 of the heterocycle were isolated instead of the expected imines. The detailed study of the transformation, including EPR experiments, revealed the most probable radical mechanism. The proposed reaction pathways were confirmed by quantum chemical calculations. The dichotomy of 1–2 and 2–3 bonds cleavage is discussed together with the evaluation of the stereochemical outcome of the reactions. The benzoazoles obtained via the new reaction are of particular interest for the medicinal chemistry. © 2020 Wiley-VCH GmbH

Chernyshov V.V. , Yarovaya O.I. , Vatsadze S.Z. , Borisevich S.S. , Trukhan S.N. , Gatilov Y.V. , Peshkov R.Y. , Eltsov I.V. , Martyanov O.N. , Salakhutdinov N.F.
Unexpected Ring Opening During the Imination of Camphor-Type Bicyclic Ketones
European Journal of Organic Chemistry. 2021. V.2021. N3. P.452-463. DOI: 10.1002/ejoc.202001397 WOS Scopus РИНЦ

Published online:	Dec 27, 2020
Published print:	Jan 22, 2021

Web of science	WOS:000602604300001
Scopus	2-s2.0-85097617232
Elibrary	45079129
OpenAlex	W3102924898