Bin Yang

Polyethylene terephthalate (PET) is widely used in daily life due to its excellent properties.

A diphenylphosphinic acid‐catalyzed and Tf ₂ O‐promoted intermolecular condensation of β ‐keto ester compounds is developed. The catalytic amount of diphenylphosphinic acid can significantly enhance the reaction efficiency, enabling the isolation of a variety of γ ‐pyrone products in good to high yields. Several control experiments provided key insights into the mechanism, revealing the dual role of diphenylphosphinic acid: it acts not only as a Brønsted acid catalyst to accelerate the reaction but also as a Lewis base to capture the alkyl group. Furthermore, this reaction can be successfully scaled up without loss of efficiency, demonstrating its potential for large‐scale industrial applications.

A metal-free electrophilic phosphination protocol utilizing silyl enol ethers as soft carbon nucleophiles has been developed under Tf₂O/DMSO-mediated conditions. This approach enables convenient access to a diverse range of β-ketophosphine oxides under mild reaction conditions. The broad substrate scope, scalability, and potential for further synthetic applications highlight the practical utility of this method. The development of this method also expands the scope of the umpolung electrophilic phosphination strategies.

We have developed an umpolung method utilizing the Tf₂O/DMSO-based system for C(sp²)-P bond or C(sp³)-P bond formation. This method employs both P(O)-H and P(O)-OH compounds as phosphorus sources and demonstrates excellent compatibility with a wide range of Grignard reagents. Without the requirement of precious transition metals or additives, this one-pot protocol provides a practical and efficient synthetic pathway to a variety of aryl and alkyl phosphine oxides. The broad substrate scope and diverse synthetic applications highlight the practical utility of this method.

A DMSO-catalyzed double P-O bond or double P-S bond formation of phosphinic acid with an O- or S-containing nucleophile has been developed. Under metal-free and mild conditions, this simple procedure provides a compatible and rapid access to a variety of phosphonates and dithiophosphates. The DFT calculation of stabilization energy (SE) and the mechanism studies demonstrated that the "just right" Lewis base property and the relatively "soft" interaction strength with the phosphenium-dication ensure the unique catalytic activity of DMSO in this transformation.

We have developed a Tf₂O-mediated approach for the direct amination of either P(O)-OH or P(O)-H reagents with a variety of aliphatic or aromatic amines. Without the requirement of precious metals and toxic reagents, this protocol provides an alternative route to various phosphinamides and phosphoramides. The reaction proceeds under simple and mild conditions and can be effectively scaled up with similar efficiency.

Sulfonyl chlorides are a class of cheap and readily available basic chemicals, which have routinely served as electrophilic reagents in their chemical transformations. Herein, we disclose a novel PPh₃‐mediated nucleophilic sulfonation method of sulfonyl chlorides with arynes. Different from the classical P(III)‐mediated reductive deoxygenation reaction of sulfonyl chlorides, the valence state of the sulfur atom has not been changed. This protocol exhibits broad functional group tolerance and provides a direct approach to a variety of aryl and alkyl sulfones.

A metal-free method for the dual activation of aryl phosphinate has been developed; the P–H and P–O bonds are sequentially activated by the Tf₂O/DMSO system. Without the requirement of metals and unstable P-reagents, this one-pot procedure provides a convenient and practical access to a variety of aryl phosphonates. A mechanism involving twice generation of electrophilic P-species and two S_N-processes is proposed on the basis of the control experiments.

A promoter‐free chalcogenophosphorylation reaction between diverse P(O)−H reagents and chalcogenosulfonates has been developed. In the absence of metal or any other additives, these transformations proceed through a spontaneous process at room temperature, which provide a convenient and compatible approach to a broad range of selenophosphates and thiophosphates. magnified image