Details

Autor(en) / Beteiligte

• Kuzmin, Julius
• Röckl, Johannes
• Schwarz, Nils
• Djossou, Jonas
• Ahumada, Guillermo
• Ahlquist, Mårten
• Lundberg, Helena

Titel

Electroreductive Desulfurative Transformations with Thioethers as Alkyl Radical Precursors

Ist Teil von

• Angewandte Chemie International Edition, 2023-09, Vol.62 (39), p.e202304272-n/a

Auflage

International ed. in English

Ort / Verlag

Germany: Wiley Subscription Services, Inc

Erscheinungsjahr

2023

Link zum Volltext

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• Thioethers are highly prevalent functional groups in organic compounds of natural and synthetic origin but remain remarkably underexplored as starting materials in desulfurative transformations. As such, new synthetic methods are highly desirable to unlock the potential of the compound class. In this vein, electrochemistry is an ideal tool to enable new reactivity and selectivity under mild conditions. Herein, we demonstrate the efficient use of aryl alkyl thioethers as alkyl radical precursors in electroreductive transformations, along with mechanistic details. The transformations proceed with complete selectivity for C(sp3)−S bond cleavage, orthogonal to that of established transition metal‐catalyzed two‐electron routes. We showcase a hydrodesulfurization protocol with broad functional group tolerance, the first example of desulfurative C(sp3)−C(sp3) bond formation in Giese‐type cross‐coupling and the first protocol for electrocarboxylation of synthetic relevance with thioethers as starting materials. Finally, the compound class is shown to outcompete their well‐established sulfone analogues as alkyl radical precursors, demonstrating their synthetic potential for future desulfurative transformations in a one‐electron manifold. Aryl alkyl thioethers are an underutilized class of alkyl radical precursors that are demonstrated to outperform their well‐established sulfone analogues under electroreductive conditions. Single electron transfer results in C−S bond cleavage and alkyl radicals that may react in C(sp3)−C(sp3) bond forming events or undergo radical‐polar crossover, followed by protonation or carboxylation to furnish alkanes or arylacetic acids.