Expanding Stereoelectronic Limits of endo-tet Cyclizations: Synthesis of Benz[b]azepines from Donor–Acceptor Cyclopropanes

Expanding Stereoelectronic Limits of endo-tet Cyclizations: Synthesis of Benz[b]azepines from Donor–Acceptor Cyclopropanes Научная публикация

Журнал

Journal of the American Chemical Society
ISSN: 0002-7863 , E-ISSN: 1520-5126

Вых. Данные

Год: 2021, Том: 143, Номер: 34, Страницы: 13952-13961 Страниц : 10 DOI: 10.1021/jacs.1c07088

Авторы

Vartanova Anna E ^1,2 , Plodukhin Andrey Yu ³ , Ratmanova Nina K ⁴ , Andreev Ivan A ^4,2 , Anisimov Mikhail N ^5,6 , Gudimchuk Nikita B ^5,6 , Rybakov Victor B ³ , Levina Irina I ⁷ , Ivanova Olga A ^3,2 , Trushkov Igor V ² , Alabugin Igor V ⁸

Организации

1	Faculty of Science, RUDN University, Moscow 117198, Russian Federation
2	N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 119334, Russian Federation
3	Department of Chemistry, M. V. Lomonosov Moscow State University, Moscow 119991, Russian Federation
4	Dmitry Rogachev National Medical Research Center of Pediatric Hematology, Oncology, and Immunology, Moscow 117997, Russian Federation
5	Center for Theoretical Problems of Physicochemical Pharmacology, Moscow 119334, Russian Federation
6	Department of Physics, M. V. Lomonosov Moscow State University, Moscow 119991, Russian Federation
7	Institute of Biochemical Physics, Russian Academy of Sciences, Moscow 119334, Russian Federation
8	Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306-4390 United States

The importance of intramolecular constraints in cyclic transition-state geometries is especially pronounced in n-endo-tet cyclizations, where the usual backside approach of a nucleophile to the breaking bond is impossible for the rings containing less than eight atoms. Herein, we expand the limits of endo-tet cyclizations and show that donor–acceptor cyclopropanes can provide a seven-membered ring via a genuine 6-endo-tet process. Substrates containing a N-alkyl-N-arylcarbamoyl moiety as an acceptor group undergo Lewis acid-induced cyclization to form tetrahydrobenz[b]azepin-2-ones in high yields. The reaction proceeds with the inversion of the configuration at the electrophilic carbon. In this process, a formally six-membered transition state yields a seven-membered ring as the pre-existing cycle is merged into the forming ring. The stereochemistry of the products can be controlled by the reaction time and by the nature of Lewis acid, opening access to both diastereomers by tuning of the reaction conditions.

Vartanova A.E. , Plodukhin A.Y. , Ratmanova N.K. , Andreev I.A. , Anisimov M.N. , Gudimchuk N.B. , Rybakov V.B. , Levina I.I. , Ivanova O.A. , Trushkov I.V. , Alabugin I.V.
Expanding Stereoelectronic Limits of endo-tet Cyclizations: Synthesis of Benz[b]azepines from Donor–Acceptor Cyclopropanes
Journal of the American Chemical Society. 2021. V.143. N34. P.13952-13961. DOI: 10.1021/jacs.1c07088 WOS Scopus OpenAlex

Web of science:	WOS:000704514200054
Scopus:	2-s2.0-85114136524
OpenAlex:	W3195169289

БД	Цитирований
OpenAlex	41
Scopus	36
Web of science	32