Abstract: A new process of “inverted” formal [3 + 2]-cycloaddition of donor–acceptor cyclopropanes (DACs) to allylic systems to give polyfunctionalized cyclopentanes has been developed. Unlike the classical version of formal [3 + 2]-cycloaddition, a DAC acts in this process as a two-carbon synthon (1,2-zwitterionic reactivity type), while an alkene acts as a three-carbon synthon. Tetramethylethylene, allylbenzenes, homoallylbenzene, terminal and internal aliphatic alkenes, and methylenecyclobutane were successfully used as alkenes. Furthermore, in order to suppress annulation at the aromatic ring in 2-arylcyclopropane-1,1-dicarboxylates and enhance the selectivity of the reaction with the allylic system of alkenes, we suggested a new approach for managing the reactivity of DACs involving substitution at both ortho positions of the aromatic ring. Multinuclear NMR spectroscopy was used to study the structure of the 1,2-zwitterionic gallium complexes generated and their properties and to examine the mechanisms of the occurring reactions.

Cite: Zotova M.A. , Novikov R.A. , Shulishov E.V. , Tomilov Y.V.
GaCl3-Mediated “Inverted” Formal [3 + 2]-Cycloaddition of Donor–Acceptor Cyclopropanes to Allylic Systems
Journal of Organic Chemistry. 2018. V.83. N15. P.8193-8207. DOI: 10.1021/acs.joc.8b00959 WOS Scopus OpenAlex

Identifiers:

≡ Web of science:	WOS:000441112900057
≡ Scopus:	2-s2.0-85049412894
≡ OpenAlex:	W2810130690

Altmetrics: