Paracyclophane derivatives in frustrated Lewis pair chemistry

The metal-free activation of hydrogen was achieved using [2.2]paracyclophane-derived bisphosphines as Lewis base in frustrated Lewis pair chemistry. The rigid scaffold allows the orientation of functional groups so that steric aspects can be studied without altering the electronic nature. Depending on the geometry, structurally different phosphonium hydridoborates were generated when the frustrated Lewis pairs were exposed to hydrogen. The bisphosphines were applied in the 1,4-hydrosilylation-hydrogenation domino reaction providing access to secondary silyl-protected alcohols from enones in one step. Additionally, the planar-chiral scaffold was applied for the synthesis of novel enantiopure Lewis acids and Lewis bases.