ja6b03215_si_003.cif (32.23 kB)

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

Download (32.23 kB)
posted on 10.05.2016, 00:00 by Liye Chen, Peng Ren, Brad P. Carrow
We report here the remarkable properties of PAd3, a crystalline air-stable solid accessible through a scalable SN1 reaction. Spectroscopic data reveal that PAd3, 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 PAd3 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 × 104 turnovers in 10 min.