Cascade Vinylation/8π-Electrocyclization and Cu(II)-Catalyzed Dehydrogenation toward Highly Stable Formally Antiaromatic Cycloheptatrienyl Anions

Cascade Vinylation/8π-Electrocyclization and Cu(II)-Catalyzed Dehydrogenation toward Highly Stable Formally Antiaromatic Cycloheptatrienyl Anions Full article

Journal

Journal of Organic Chemistry
ISSN: 1520-6904 , E-ISSN: 0022-3263

Output data

Year: 2023, Volume: 88, Number: 9, Pages: 5661-5670 Pages count : 10 DOI: 10.1021/acs.joc.3c00142

Authors

Ilyushchenko Matvey K ^1,2 , Salikov Rinat F ² , Sokolova Alena D ² , Litvinenko Veronika V ² , Belyy Alexander Yu ² , Platonov Dmitry N ² , Tomilov Yury V ²

Affiliations

1	Lomonosov Moscow State University, Leninskie Gory GSP-1,1−3, 119991 Moscow, Russian Federation
2	N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Prospect, 119991 Moscow, Russian Federation

An approach to the synthesis of seven-membered systems via the chain elongation of nucleophilic propenes and subsequent 8π-electrocyclization is proposed. The cascade reaction yields either cycloheptadienes or bicycloheptenes, and the latter are formed via a 6π-electrocyclization of intermediate cycloheptadienyl anion which was proved to be reversible in a basic medium. The electrocyclic nature of the ring-closing reactions was supported by density functional theory and DLPNO/CCSD(T) calculations. Highly electron-deficient cycloheptatrienes can be obtained from cycloheptadienes or bicycloheptenes via oxidation either introduced into the cascade reaction or performed as a separate reaction, with the overall yield of up to 81%. The oxidation step was performed by means of a rarely encountered Cu(II)-catalyzed dehydrogenation of cycloheptadienes or bicycloheptenes, and so the reaction mechanism was proposed. Stable formally 8π-antiaromatic cycloheptatrienyl-anion containing compounds were obtained, and some correlations between their UV–vis spectra and the structure of the distorted cycloheptatrienyl-anion moiety were clarified. Additionally, a base-induced retro-[2 + 2]-cycloaddition in a bicycloheptene derivative gave cyanotetra(methoxycarbonyl)cyclopentadienyl cesium.

Ilyushchenko M.K. , Salikov R.F. , Sokolova A.D. , Litvinenko V.V. , Belyy A.Y. , Platonov D.N. , Tomilov Y.V.
Cascade Vinylation/8π-Electrocyclization and Cu(II)-Catalyzed Dehydrogenation toward Highly Stable Formally Antiaromatic Cycloheptatrienyl Anions
Journal of Organic Chemistry. 2023. V.88. N9. P.5661-5670. DOI: 10.1021/acs.joc.3c00142 WOS Scopus OpenAlex

≡ Web of science:	WOS:001091871700001
≡ Scopus:	2-s2.0-85152134187
≡ OpenAlex:	W4362693022