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A 1,2‐dihydrophosphination of bis(phenylphosphino)ethane with a wide range of activated olefins was achieved in a catalytic manner with enantiomeric and diastereomeric excess of up to >99% and 44% respectively. The protocol can be extended to selected substrates leading to free P‐ and C‐chiral 1,2‐diphosphines. The synthesized ligands can also undergo direct complexation onto palladium affording complexes with complete retention of stereo‐integrity. [ABSTRACT FROM AUTHOR]

An iron‐mediated ring‐opening and rearrangement cascade from 4‐alkenylisoxazoles to polysubstituted pyrroles is described. The cascade reaction conditions are compatible with a variety of functional groups, including ketones, esters, amides, and aryl halides. High reactivity is maintained even if the reaction scale is expanded to 0.5 grams. It is the first iron‐catalyzed rearrangement of 4‐alkenylisoxazoles to pyrroles that is independent of the presence of the alkoxy or amino group at position 5 of the isoxazole substrates. A plausible mechanism of the iron‐mediated cascade reaction is proposed. [ABSTRACT FROM AUTHOR]

The catalytic hydrophosphination reaction is one of the most sustainable chemical transformations today. Here, the palladium-catalyzed asymmetric PH addition of diarylphosphines with N-enoylbenzotriazoles and analogues is described. Chiral phosphine products are obtained in 100% atom economy and without cumbersome protection-deprotection manipulations. The obtained products can be subsequently transformed to bear various functionalities, including phosphino-carboxylic esters which play critical roles in catalysis and as synthetic aids. Anti-tumour activities of the corresponding gold-phosphine complexes have been explored, contributing to existing chemotherapeutic research in cancer treatment. [ABSTRACT FROM AUTHOR]