Vinylcyclopropane-Cyclopentene (VCP-CP) Rearrangement Enabled by Pyridine-Assisted Boronyl Radical Catalysis.

An unprecedented VCP-CP (vinylcyclopropane-cyclopentene) rearrangement approach has been established herein by virtue of the pyridine-boronyl radical catalyzed intramolecular ring expansions. This metal-free radical pathway harnesses readily available catalysts and unactivated vinylcyclopropane starting materials, providing an array of cyclopentene derivatives chemoselectively under relatively mild conditions. Mechanistic studies support the idea that the boronyl radical engages in the generation of allylic/ketyl radical species, thus inducing the ring opening of cyclopropanes and the following intramolecular cyclization processes.

Copper Difluorocarbene Enables Catalytic Difluoromethylation.

Despite the synthetic versatility of difluorocarbene, its high reactivity severely regulates widespread applications of difluorocarbene in organic synthesis. Here, we report a copper difluorocarbene-involved catalytic coupling, representing a new mode of the difluoromethylation reaction. This method allows difluoromethylation of a wide range of readily available allyl/propargyl electrophiles with NaBH3CN and low-cost difluorocarbene precursor BrCF2CO2K, featuring high cost-efficiency, high stereo- and regioselectivities, and high functional group tolerance, even with complex drug-like molecules. Applying the method led to the efficient synthesis of deuterated difluoromethylated compounds of medicinal interest. The resulting difluoromethylated allyl and allenyl products can serve as versatile synthons for diverse transformations, rendering the approach attractive for synthesizing complex fluorinated structures. Experimental mechanistic studies and computational calculations reveal that the formation of a difluoromethylcopper(I) intermediate through the nucleophilic attack of boron hydride on the copper(I) difluorocarbene is the key step in the reaction.

A visible-light-induced bromine radical initiates direct C-H alkylation of heteroaromatics.

Herein, a photoinduced direct C(sp2)-H alkylation of N-heteroaromatics by using commercially available tetrabutylammonium tribromide (TBATB) as a HAT reagent is described. The method uses O2 as the oxidant, and features metal-free, mild reaction conditions and good functional group compatibility.

Visible light-induced metal-free chemoselective oxidative cleavage of benzyl C-heteroatom (N, S, Se) bonds utilizing organoboron photocatalysts.

The oxidation process is widely explored and used to synthesize diverse organic chemicals. Herein, a unified metal-free photooxidative platform for the cleavage of C-heteroatom bonds has been developed. In these reactions, the aminoquinolate diarylboron (AQDAB) complex is utilized as the photocatalyst, instigating the oxidation process induced by visible light. The cleavage of C-heteroatom bonds can be achieved chemoselectively, affording the formal carbonylation product of C-N, C-S, and C-Se bonds. This method provides a channel for connecting amines, thiols, or selenides with the carbonyl compounds directly, broadening the potential applications of oxidation as a synthetic tool.

Visible Light-Mediated Organoboron-Catalyzed Metal-Free Synthesis of Silanols from Silanes.

Herein, a four-coordinated organoboron compound, aminoquinoline diarylboron (AQDAB), is utilized as the photocatalyst in the oxidation of silane to silanol. This strategy effectively oxidizes Si-H bonds, affording Si-O bonds. Generally, the corresponding silanols can be obtained in moderate to good yields at room temperature under oxygen atmospheres, representing a green protocol to complement the existing preparation methods for silanols.

Dual aminoquinolate diarylboron and nickel catalysed metallaphotoredox platform for carbon-oxygen bond construction.

Herein, aminoquinolate diarylboron complexes are utilized as photocatalysts in dual Ni/photoredox catalyzed carbon-oxygen construction reactions. Via this unified metallaphotoredox platform, diverse (hetero)aryl halides can be conveniently coupled with acids, alcohols and water. This method features operational simplicity, broad substrate scope and good compatibility with functional groups.