title: Tri(1-adamantyl)phosphine: Expanding the Boundary of Electron-Releasing Character Available to Organophosphorus Compounds.
abstract: 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 × 10(4) turnovers in 10 min.
authors.affiliation: Department of Chemistry, Princeton University , Princeton, New Jersey 08544, United States.
authors.forename: Liye
authors.initials: L
authors.lastname: Chen
authors.affiliation: Department of Chemistry, Princeton University , Princeton, New Jersey 08544, United States.
authors.forename: Peng
authors.initials: P
authors.lastname: Ren
authors.affiliation: Department of Chemistry, Princeton University , Princeton, New Jersey 08544, United States.
authors.forename: Brad P
authors.initials: BP
authors.lastname: Carrow
mesh_terms: D002384:Catalysis; D004583:Electrons; D006571:Heterocyclic Compounds / Q000737:chemistry; D008697:Methane / Q000031:analogs & derivatives / Q000737:chemistry; D009943:Organophosphorus Compounds / Q000737:chemistry*; D010720:Phosphines / Q000737:chemistry*
chemical_list: D006571:Heterocyclic Compounds; D009943:Organophosphorus Compounds; D010720:Phosphines; C030011:carbene; C044646:phosphine; D008697:Methane