Work

Aryl iodane-induced cascade arylation–1,2-silyl shift–heterocyclization of propargylsilanes under copper catalysis

Year: 2025

Type: article

Abstract: A novel copper-catalyzed arylation strategy for propargylsilanes utilizing diaryl-λ 3 -iodanes has been developed, enabling a cascade sequence involving 1,2-silyl migration and heterocyclization. The β-silicon effect facilitates the formation of stabilized allyl cation intermediates that undergo regioselective trapping by internal O - and N -nucleophiles furnishing functionalized heterocycles. This method provides access to tetrahydrofuran or pyrrolidine frameworks, each bearing a trifunctionalized ( E )-configured vinyl side chain. The use of a shorter linker provides entry to 1,2,3,6-tetrahydropyridines. Additionally, in the absence of internal nucleophiles, this methodology yields aryl-substituted 1,3-dienes. This work introduces a palladium-free, single-step alternative to multistep heterocycle construction from propargylsilanes and highlights the synthetic potential of iodane-mediated carbofunctionalization under copper catalysis.

Source: Beilstein Journal of Organic Chemistry

DOI: 10.3762/bjoc.21.154

Authors: Rasma Kroņkalne, Rūdolfs Beļaunieks, Armands Sebris, Anatoly Mishnev, Māris Turks

Institutions: Riga Technical University, Latvijas Organiskās Sintēzes Institūts

Language: English

Topic: Catalytic Cross-Coupling Reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: diamond

Funder: Latvijas Zinātnes Padome

Award: 1,2-Sililnobīde propargilsilānos kā jauna metodoloģija farmaceitiski svarīgu heterociklu un aizvietotu olefīnu sintēzei