Dialkylchlorophosphines are among the most versatile building blocks for tertiary phosphine ligands, but their synthesis relies on the nucleophilic substitution of PCl3, leaving substituents that require P-H precursors largely inaccessible. The primary phosphine reagent iPr2NPH2·BH3 can serve as a doubly protected PH2Cl proxy, enabling the synthesis of bis(bicyclo[1.1.1]pentyl)chlorophosphine (Bcp2PCl) for the first time. Bcp2PCl serves as a general reagent for the preparation of a family of bis(bicyclo[1.1.1]pentyl) alkyl- and arylphosphines, including new members of privileged phosphine ligand scaffolds.