Palladium was found to catalyze regioselective Markovnikov addition of chiral enantiopure 1r-oxo-2c,5t-diphenylphospholane (1) to terminal alkynes, whereas rhodium catalysis offers selectively the (E)-anti-Markovnikov adduct. ThisSupporting Information (see footnote on the first page of this article): Experimental procedures, characterization data and copies of the 1 H, 13 C and 31 P NMR spectra.www.eurjoc.org

Chiral enantiopure 1-alkyl-2,5-diphenylphospholanium salts were obtained in one step through alkylation of phospholane with alkyl triflates. The resulting air-stable phosphonium salts are electron-rich trialkylphosphane precursor ligands for transition metals, and they offer a convenient route to-

Chiral enantiopure 2‐5‐diphenylphospholane borane 8 is an interesting nucleophile for allylic phosphination in the presence of palladium complexes to form CP bonds. A highly diastereoselective allylic phosphination reaction was realized using chiral palladium‐DACH‐naphthyl (DACH=1,2‐diaminocyclohexane) ligand as the catalyst system. The secondary phosphine‐borane complex could be classified as a NuL type nucleophile.