Tri(1-adamantyl)phosphine: Expanding the Boundary of Electron-Releasing Character Available to Organophosphorus Compounds

摘要

We report here the remarkable properties of PAd_3, a crystalline air-stable solid accessible through a scalable S_N1 reaction. Spectroscopic data reveal that PAd_3, benefiting from the polarizability inherent to large hydrocarbyl groups, exhibits unexpected electron releasing character that exceeds other alkylphosphines and falls within a range dominated by N-heterocyclic carbenes. Dramatic effects in catalysis are also enabled by PAd_3 during Suzuki-Miyaura cross-coupling of chloro(hetero)-arenes (40 examples) at low Pd loading, including the late-stage functionalization of commercial drugs. Exceptional space-time yields are demonstrated for the syntheses of industrial precursors to valsartan and boscalid from chloroarenes with ～2 × 10~4 turnovers in 10 min.