The p-stereogenic alkynylphosphines couple a conformationally well-defined phosphorus center with a linear carbon--carbon triple bond, ready for further functionalization. The synthesis of p-stereogenic alkynylphosphines requires challenging methodology because bromoalkynes can react directly with secondary phosphines, while stereoselective synthesis requires selective formation of a C(sp)--P bond within a chiral metal complex. As we have developed previously, the nickel-catalyzed procedure utilizes bench stable secondary phosphine oxides, in situ reduction using phenylsilane, Ni(COD)2/(S,S)-Et-Duphos catalyst, sodium acetate, mesitylene, and reaction temperature of $0~^\circ\mathrm{C}$ for 72 h. This protocol enables formation of p-stereogenic alkynylphosphines from the tert-butyl phenyl phosphorus component in 72\% isolated yield and 86\% ee versus 20\% product without nickel catalyst. The first group of substituent analysis identifies the role of steric hindrance at phosphorus where the phenyl/ethyl substrate yields 81\% yield and 29\% ee versus phenyl/tert-butyl substrate, providing slightly reduced yield and enhanced enantiomeric excess. The series of secondary phosphine oxide substrates comprises para-, meta- and ortho-substituted aryl tert-butyl derivatives, giving rise to products such as 3fa--3ka in 63--78\% yield and 76--90\% ee, 3la in 64\% yield and 75\% ee, 3ma in 70\% yield and 82\% ee, and 3na in 68\% yield and 90\% ee. Bromoalkyne substrates range from variously substituted aryl, heteroaryl, naphthyl, alkyl, bis-alkynyl, to amino acid derived electrophiles. Examples are the product 3na-O in 64\% yield and 90\% ee, 3nk in 33\% yield, 97\% ee, and 5:1 diastereomeric ratio, and 3no in 32\% yield and 9:1 diastereomeric ratio. Further derivatizations include hydration of 3na-O affording a $\beta$-keto phosphine derivative in 73\% yield and 84\% ee, radical cyclization of 3ba resulting in benzo[b]phosphole oxide in 58\% yield, 86\% ee, and 3:1 diastereomeric ratio, and formation of phosphhepine from 3wp providing compound with 99\% ee upon recrystallization. Reaction works when bond formation by means of the nickel catalyst takes place in the predominant mode, the phosphorus groups show enough difference in their stereochemistry, and the alkyne group remains intact for further applications in carbonyl, heterocyclic, and chiroptical phosphorus chemistry.

P-stereogenic phosphorus,alkynylphosphines,nickel catalysis,asymmetric cross-coupling,C(sp)--P bond formation,phosphole oxide,phosphepine,circularly polarized luminescence