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Electrophotocatalysis Versus Indirect Electrolysis: Electrochemical Selenocyclization of 3-Aza-1,5-dienes Facilitated by Energy Transfer, Direct Photolysis or N-Hydroxyphthalimide.

Chemistry

June 2024

Yunnan Key Laboratory of Metal-Organic Molecular Materials and Device, School of Chemistry and Chemical Engineering, Kunming University, 2 Puxin Road, Kunming, 650214, China.

Three hybrid electrochemical protocols, which involve the energy transfer, direct photolysis and N-hydroxyphthalimide catalyst, respectively, are presented for the selenylation/cyclization of the fragile substrates of 3-aza-1,5-dienes with diorganyl diselenides to afford 3-selenomethyl-4-pyrrolin-2-ones. The two electrophotocatalytic reactions and the indirect electrolysis one are both regioselective and external-oxidant- and transition-metal-free, and are associated with a broad substrate scope and high Se-economy, and all three methods are amenable to gram-scale syntheses, late-stage functionalizations, sunlight-induced experiments and all-solar-driven syntheses.

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Selenium-containing compounds are important scaffolds owing to their value in medicinal chemistry, biochemistry and material chemistry. Herein, we report an electrochemical approach to access seleno-benzazepines through an oxidative radical cascade cyclization of dienes with diselenides under metal-free, external oxidant-free and base-free conditions. In a simple undivided cell, various dienes and diselenides were suitable for this transformation, generating the desired products in up to 84% yields.

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Article Synopsis
  • The text discusses a method for adding two functional groups to 1,3-dienes using a photoinduced copper catalyst.
  • This process involves generating a selenium atom radical through visible light, which reacts to form an allyl radical intermediate.
  • The allyl radical can then quickly isomerize and undergo copper-catalyzed reactions with different nucleophiles, allowing for selective functionalization.
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A cascade selenylation/cyclization of dienes with diselenides has been realized under visible-light irradiation or electrolysis conditions. Employing O or electricity as a "green" oxidant, this protocol provides a green and efficient method for an array of biologically important seleno-benzo[]azepine derivatives in moderate to good yields. The direct sunlight irradiation and gram-scale reaction render the approach practical and attractive.

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Three-Component Electrochemical Aminoselenation of 1,3-Dienes.

J Org Chem

May 2023

State Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources, School of Chemistry and Pharmaceutical Sciences of Guangxi Normal University, Guilin 541004, People's Republic of China.

Azoles and organoselenium compounds are pharmacologically important scaffolds in medicinal chemistry and natural products. We developed an efficient regioselective electrochemical aminoselenation reaction of 1,3-dienes, azoles, and diselenide derivatives to access selenium-containing allylazoles skeletons. This protocol is more economical and environmentally friendly and features a broad substrate scope; pyrazole, triazole, and tetrazolium were all tolerated under the standard conditions, which could be applied to the expedient synthesis of bioactive molecules and in the pharmaceutical industry.

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