A new anode strategy for accessing xanthen-9azoles via an electrochemical C(sp 3 )−H/N−H cross-coupling of xanthenes with azoles is described. This reaction proceeds efficiently with a broad scope of both xanthenes and N−H-free azoles under metal-and additional oxidant-free conditions and represents a new access to direct incorporation of important N-heterocycle units into the resulting xanthenes.X anthen-9-amines are important motifs existing in many important biologically active molecules, pharmaceuticals, and materials and find increasing applications in synthesis (Figure 1). 1−3 Accordingly, developing elegant approaches for construction of these molecules remains an ongoing point of interest for synthetic chemists. Traditional methods include transition-metal-catalyzed C−H amination 4 of xanthenes with nitrene precursors, which has emerged as the most common tool for the synthesis of xanthen-9-amines. However, such transformations suffer from heavy metal residues, toxic waste, and substrate prefunctionalization (Scheme 1a). Alternatively, the dehydrogenative cross-coupling reaction 5 is particularly attractive owing to its avoidance of the substrate prefunctionalization with highly atom-economy to construct various carbon−carbon bonds 6 and carbon−heteroatom bonds. 7 Among them, the direct C−H/N−H dehydrogenative crosscoupling of xanthenes represents one of the most efficient methods for accessing xanthen-9-amines. 8 However, most of these strategies require a combination of transition metals and excess amounts of external oxidants. Thus, there is an urgent need for developing improved synthetic pathways that can address these shortcomings.Recently, Zeng and co-workers developed an intermolecular electrochemical C(sp 3 )−H/N−H cross-coupling of xanthenes with amides to produce N-alkoxy-N-(9H-xanthen-9-yl)benzamide using 0.5 equiv of ferrocene as the redox catalyst under basic conditions (Scheme 1b). 9 Although this method has provided a conceptually novel strategy for the C(sp 3 )−N bond formation, it is restricted to narrow substrate scope with respect to only four examples of 9H-xanthene as well a special N-alkoxybenzamide. We envisioned that by employing the anodic oxidant the C(sp 3 )−H/N−H cross-coupling 10−12 might proceed successfully to enable the formation of the C−N bond under redox catalyst free conditions. Herein, we report a new anode strategy for the synthesis of xanthen-9azole derivatives (Scheme 1c) by C(sp 3 )−H/N−H dehydrogenative cross-coupling of xanthenes with various N−H-free azoles (e.g., 1H-indazoles, 1H-pyrazoles, 4H-pyrazolo-[3,4-

Radical‐initiated difunctionalization of alkenes is one of the most important methods in organic synthesis and medicinal chemistry, which can be applied to synthesize value complex compounds as well as structural motifs that found in bioactive natural products and pharmaceuticals. In recent years, impressive progress have been made in this area with ideal silver catalysis. Here, we summarize recent advances in silver‐mediated radical difunctionalization of alkenes for the formation of diverse bonds, including 1) two‐component radical difunctionalization reactions enabled by an intramolecular cyclization process toward various cyclic compounds and 2) three‐component radical difunctionalization reactions leading to complex linear compounds. These silver‐mediated radical alkene difunctionalization transformations are general initiated by different radicals, such as carbon‐, oxygen‐, sulfur‐, phosphinyl‐, and halogen‐center radicals, followed by terminated with nucleophiles to form two new bonds in a single reaction.

An oxidant-free electrochemical dehydrogenative cross-coupling of xanthenes and ketones for the preparation of functionalized 9-alkyl-9H-xanthenes was developed.

C(sp3)-H arylation has recently emerged as a powerful straegy for complex organic molecules synthesis through a new carbon-carbon bond formation. We herein describe an efficient electrochemical C(sp3)-H arylation of xanthenes...