Synthesis of Bicyclo[1.1.1]pentane (BCP)‐Based Straight‐Shaped Diphosphine Ligands**

Abstract [1.1.1]Propellane, which is structurally simple and compact, exhibits promising potential for the synthesis of disubstituted straight‐shaped bicyclo[1.1.1]pentane (BCP) compounds by manipulation of its highly reactive internal C−C bond. BCPs are considered to be isosteres of 1,4‐disubstituted benzenes, which have found broad applications in the areas of functional molecules and drug discovery. The internal C−C single bond of [1.1.1]propellane is regarded as a charge‐shift bond, which can be readily cleaved by radical means to construct BCPs. We herein report a novel synthetic method for (un)symmetric diphosphines based on the BCP motif, which can be interpreted as isosteres of 1,4‐bis(diphenylphosphino)benzenes. The obtained BCP‐diphosphine derivatives were used to generate a straight‐shaped Au complex and an Eu‐based coordination polymer.