Methodologies for the effective fabrication of phosphinothioates, phosphonothioates, and phosphorothioates have always been of great interest due to their widespread application in many research fields. We present here a solvent-free reaction system for the synthesis of above compounds without any catalysts or additives, directly using disulfides with diarylphosphine oxides, dialkylphosphites, and phosphinates as substrates. Most of the target compounds were obtained in nearly quantitative yields by heating at 50 °C for 5–10 min or stirring at room temperature for 3 h. The products were efficiently separated via a water extraction operation, simultaneously recovering the by-product thiols. This mild and practical coupling protocol was also employed to prepare phosphinoselenoates from the corresponding diselenides with good yields.

A novel and controllable synthesis of thioacetals/thioketals and β-sulfanyl ketones mediated by the reaction of aldehyde/acetone with thiols has been developed. In this protocol, β-sulfanyl ketones can be generated without the prior preparation of α, β-unsaturated carbonyl compounds. A variety of thiols reacted with aldehyde/acetone and provided the corresponding thioacetals/thioketals and β-sulfanyl ketones in good to excellent yields, respectively. This protocol is operationally simple, mild, and atom-economical, providing controllable access to thioacetals/thioketals and thia-Michael addition products under mild conditions.

Functionalized imidazo[1,2-α]pyridines are important scaffolds in pharmaceuticals. Herein, we present an efficient 3-sulfonylmethylation protocol for imidazo[1,2-α]pyridines by sodium sulfinates in DMA and H₂O (2:1) via an FeCl₃-catalyzed three-component coupling reaction. Various sulfonylmethyl imidazo[1,2-α]pyridines were thus afforded in high yields with excellent functional group tolerance. A plausible oxidation-addition mechanism was proposed.

Optically pure phosphonates featuring an α-functional motif serve as core structures of versatile pharmaceuticals. Pudovik reaction employing P-stereogenic H -phosphonates derived from recyclable chiral auxiliary (CA) is one of the most practical and efficient asymmetric synthetic strategies. Although several centre and axial CAs have been investigated in this field, the development of novel chiral H -phosphonates has remained largely unexplored over the past 25 years. Here, we developed a kind of H -phosphonate (CAMDOL-PHO) derived from camphor-derived 2,3-diol (CAMDOL). Stereoselective Pudovik reactions of CAMDOL-PHO with diverse aldehydes, aldimines, and nitroalkenes were well developed, affording a library of molecules of α-hydroxyl, α-amino, and β-nitro phosphonates respectively with high dr values (up to 99:1) and yields (up to 97%) as well as broad scopes. Comparative DFT and experimental studies demonstrated that CAMDOL-PHO possessed significant superiority to install the P-adjacent C-stereogenic centre, mainly benefiting from its unique diphenyl-substituted camphor skeleton with an angular methyl group.

The [1,2]-phospha-Brook rearrangement serves as a powerful synthetic strategy that enables efficient carbonyl umpolung through phosphoryl group migration, providing direct access to α-hydroxyphosphoryl compounds—a privileged class of synthons with broad applications in organophosphorus chemistry, medicinal chemistry, and materials science. This review provides a comprehensive overview of recent progress in synthetic methodologies, possible mechanisms, and asymmetric transformations, highlighting key breakthroughs and future directions in this rapidly evolving field.

The multifunctional linker molecules are crucial for the bio-orthogonal reaction for proteomic target profiling. Herein, we wish to present a novel type of biotin-based tetra-functional bio-orthogonal linkers 3a–3h named BPPA which, possessing a unique photolabile phenacyl ester motif, were readily prepared in 85–90% yields by a simple and green one-step protocol from commercially available and inexpensive reagents of biotin acids and 4’-ethynyl/azido 2-bromoacetophenones. The typical click reaction of BPPA linkers 3a and 3e via copper-catalyzed azide–alkyne cycloaddition (CuAAC) took place easily, resulting in the corresponding BPPA-triazole adducts 4a and 4b in nearly quantitative yields. A further cleavability evaluation of 4a and 4b demonstrated that the expected C-O bond detachment could be accomplished efficiently and rapidly by UV irradiation or by ammonia hydrolysis, respectively, resulting in the residual (hydroxyl)acetylphenyl triazole fragment supposed to be attached to proteins during biological manipulations. The BPPA linkers, with dual clickable options of either the terminal azide or alkyne clickable group, exhibit high potentials for various CuAAC-oriented bio-orthogonal reactions.