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Sulfilimines, the aza‐variants of sulfoxides, are key structural motifs in natural products, pharmaceuticals, and agrochemicals; and sulfilimine synthesis is therefore important in organic chemistry. However, methods for radical sulfilimination remain elusive, and as a result, the structural diversity of currently available sulfilimines is limited. Herein, we report the first protocol for decarboxylative radical sulfilimination reactions between sulfenamides and N‐hydroxyphthalimide esters of primary, secondary, and tertiary alkyl carboxylic acids, which were achieved via a combination of photoredox, copper, and Brønsted base catalysis. This novel protocol provided a wide variety of sulfilimines, in addition to serving as an efficient route for the synthesis of S‐alkyl/S‐aryl homocysteine sulfilimines and S‐(4‐methylphenyl) homocysteine sulfoximine. Moreover, it could be used for late‐stage introduction of a sulfilimine group into structurally complex molecules, thereby avoiding the need to preserve labile organosulfur moieties through multistep synthetic sequences. A mechanism involving photocatalytic substrate transformation and copper‐mediated C(sp3)−S bond formation is proposed. [ABSTRACT FROM AUTHOR]

Abnormal copper ions (Cu2+) and biothiols have potential impacts on environmental pollution and human health, so the detection of these substances with high selectivity and sensitivity has become an important research topic. In this study, we designed and synthesized two fluorescent probes (L 1 and L 2) based on naphthalene and anthracene derivatives that could specifically detect Cu2+ and biothiols. Owing to the paramagnetic effect of Cu2+, the strong fluorescent intensity was quenched after the addition of Cu2+. When biothiols were added to the solution (L-Cu2+), the fluorescence intensity was significantly enhanced and recovered. So, the interaction process was accompanied with "ON-OFF-ON" phenomenon in fluorescent intensity. Two complexes (L-Cu2+) showed low limit of detection for biothiols (Cys was 3.4 ×10−5 M and GSH was 2.0 ×10−5 M) and weak cytotoxicity (< 150 μg/mL). Theoretical investigation analysis revealed that the intramolecular hydrogen bond existed in the structure of probes and the roles of molecular frontier orbitals in molecular interplay. In addition, two probes also showed good applicability in actual drug Atomolan. The GSH content in the tested Atomolan reached over 99.9% of the labeling which was accord with the percentage of pharmacopoeia. Therefore, two probes have the real application value in the detection of Cu2+, biothiols and drug efficacy in various environments. • Fluorescent probes based on naphthalene and anthracene derivatives. • High selectivity and sensitivity for Cu2 + and biothiols. • Low limit of detection for biothiols and weak cytotoxicity. • Good applicability in actual drug Atomolan. [ABSTRACT FROM AUTHOR]

A variety of symmetrical thiosulfonates are synthesized via Cu‐catalyzed reductive homocoupling of aryl sulfonyl chlorides. This protocol uses organic amine acting as a mild reductant and low‐cost copper as an effective catalyst. Such a reductive coupling process features a broad substrate scope and good functional group tolerance. Related thiosulfonate products can also be converted into diverse functional molecules. [ABSTRACT FROM AUTHOR]

A cheap copper-catalyzed ligand-free, regioselective alkene allylic sulfonylation reaction has been efficiently developed employing commercially available α-methylstyrene derivatives and sulfonyl chlorides. This redox-neutral protocol can be easily scale up to a gram scale. [Display omitted] Allyl sulfones are synthesized via Cu-catalyzed ligand-free regioselective sulfonylation reaction from easily obtained α-methylstyrene derivatives and sulfonyl chlorides. This redox-neutral protocol also features a low-cost metal catalyst, broad substrate scope, good functional group tolerance and could be smoothly amplified to a gram scale. The allylic sulfone products can be used in diverse radical coupling reactions. [ABSTRACT FROM AUTHOR]

[Display omitted] A copper-catalyzed redox-neutral alkene sulfonylation reaction has been developed. This reported protocol can be easily scale up to a gram scale, and smoothly applied to the late-stage modification of several bioactive molecules. [ABSTRACT FROM AUTHOR]