Alkynylphosphines or their borane complexes are available either through C–P bond forming reactions or through modification of the phosphorus or the alkynyl function of various alkynyl phosphorus derivatives. The latter strategy, and in particular the one involving phosphoryl reduction by alanes or silanes, is the method of choice for preparing primary and secondary alkynylphosphines, while the former strategy is usually employed for the synthesis of tertiary alkynylphosphines or their borane complexes. The classical C–P bond forming methods rely on the reaction between halophosphines or their borane complexes with terminal acetylenes in the presence of a stoichiometric amount of organometallic bases, which precludes the access to alkynylphosphines bearing sensitive functional groups. In less than a decade, efficient catalytic procedures, mostly involving copper complexes and either an electrophilic or a nucleophilic phosphorus reagent, have emerged. By proceeding under mild conditions, these new methods have allowed a significant broadening of the substituent scope and structure complexity.

A versatile synthesis of 1,2,3-triazolyl-4-phosphines from the borane complexes of phosphino-alkynes is reported. The efficiency of the procedure relies on the use of readily available silyl-protected alkynylphosphine-boranes, which were subjected to desilylation with TBAF followed by copper-catalyzed azide–alkyne-cycloaddition in one pot. Subsequent treatment with DABCO afforded the targeted triazolylphosphines in high yields. The reported method was applied to the synthesis of the first example of an enantioenriched P-stereogenic triazolylphosphine (98.8% ee).