Sulfonimidamides
(SIAs) and sulfoximines (SOIs) have attracted
attention due to their potential in agriculture and in medicinal chemistry
as bioisosteres of biologically active compounds, and new synthetic
methods are needed to access and explore these compounds. Herein,
we present a light-promoted generation of perfluorinated aromatic
nitrenes, from perfluorinated azides, that subsequently are allowed
to react with sulfinamides and sulfoxides, generating achiral and
chiral SIAs and SOIs. One of the enantiopure SIAs was evaluated as
a novel chiral auxiliary in Grignard additions to the imines yielding
the product in up to 96:4 diastereomeric ratio.
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.
Herein, the use of aryl alkyl thioethers as precursors for C-centered alkyl radicals is demonstrated for desulfurative C-H and C-C bond formation under electroreductive conditions. The transformations occur with complete selectivity for C(sp3)-S bond cleavage, orthogonal to that of transition metal-catalyzed two-electron routes. Experimental and theoretical studies provide mechanistic insights that serve as a steppingstone for future use of thioethers as efficient radical precursors that can outcompete their established sulfone analogues.
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.
Herein, the use of aryl alkyl thioethers as precursors for C-centered alkyl radicals is demonstrated for desulfurative C-H and C-C bond formation under electroreductive conditions. The transformations occur with complete selectivity for C(sp3)-S bond cleavage, orthogonal to that of transition metal-catalyzed two-electron routes. Experimental and theoretical studies provide mechanistic insights that serve as a steppingstone for future use of thioethers as efficient radical precursors that can outcompete their established sulfone analogues.
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