Synthesis of Aryl Thiocyanates and Aryl Selenocyanates via Visible‐Light Activation of Arylazo Sulfones

While the emergence of electrophotochemistry provides opportunities, such a chemistry at this stage suffers from limited reaction types and high photocatalyst loadings. A self‐catalyzed electrophotosynthesis as well as one with a low photocatalyst loading is presented. These external‐oxidant‐free cyclizations are enabling and applicable to a range of activated alkenes, affording a diverse array of thiocyanato heterocycles including 4‐pyrrolin‐2‐ones, isoquinoline‐1,3‐diones, indolo[2,1‐a]isoquinolin‐6(5H)‐ones, benzoimidazo[2,1‐a]isoquinolin‐6(5H)‐ones and indolin‐2‐ones, and the protocols are amenable to the late‐stage diversification of complex molecular architectures as well as gram‐scale syntheses. Sunlight could serve as the light source, and the reaction could be conducted in an all‐solar‐driven mode using a commercially available photovoltaic panel to produce electricity.

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Synthesis of Selenium Derivatives using Organic Selenocyanates as Masked Selenols: Chemical Reduction with Rongalite as a Simpler Tool to give Nucleophilic Selenides

Castro‐Godoy,

Heredia,

Bouchet

et al. 2024

ChemPlusChem

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The chemical reduction within a family of organic selenocyanates, as masked selenols, using reducing agents, such as Rongalite, sodium dithionite, and sodium thiosulfate is investigated. Using Rongalite, the corresponding diselenides were obtained quantitatively and selectively in very good to excellent yields (51‐100%) starting from alkyl, aryl, and benzyl selenocyanates. The scope of the reaction is unaffected by the electronic nature of the substituents. Furthermore, the reducing agent, Rongalite, is compatible with hydrolysable and reducing‐sensitive functional groups. Additionally, a simple methodology employing the in‐situ generated benzyl selenolate anion (PhCH2Se‾) to promote aliphatic nucleophilic substitution, epoxide ring opening, and Michael addition reactions has been developed; thus extending the structural diversity of the synthesized selenium derivatives.

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Synthesis of Aryl Thiocyanates and Aryl Selenocyanates via Visible‐Light Activation of Arylazo Sulfones

Cited by 3 publications

References 68 publications

Arylazo sulfones: multifaceted photochemical reagents and beyond

Arylazo sulfones: multifaceted photochemical reagents and beyond

Self‐ or Acridinium‐Catalyzed Electrophotosynthesis of Thiocyanato Heterocycles from Activated Alkenes

Synthesis of Selenium Derivatives using Organic Selenocyanates as Masked Selenols: Chemical Reduction with Rongalite as a Simpler Tool to give Nucleophilic Selenides

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