title: Synthesis of an electron-rich KITPHOS monophosphine, preparation of derived metal complexes and applications in catalysis.
abstract: This protocol describes the synthesis of a representative example of the electron-rich biaryl-like KITPHOS class of monophosphine, 11-dicyclohexylphosphino-12-phenyl-9,10-dihydro-9,10-ethenoanthracene (H-KITPHOS). The bicyclic architecture of H-KITPHOS is constructed via [4+2] Diels-Alder cycloaddition between 1-(dicyclohexylphosphinoylethynyl)benzene and anthracene. H-KITPHOS monophosphine is prepared via an operationally straightforward three-step procedure and is isolated in an overall yield of ∼55%. The synthesis of palladium and gold precatalysts of H-KITPHOS are also described; the yields of analytically pure complexes are high (75-85% and 85-90%, respectively). The palladium complex of H-KITPHOS forms a highly active catalyst for C-C and C-N cross-coupling of a range of aryl and heteroaryl chlorides and bromides, and the electrophilic Lewis acid gold complex efficiently catalyzes a host of cycloisomerizations. The total time required for the synthesis of H-KITPHOS is 95 h; the preparation of corresponding palladium and gold precatalysts requires an additional 7-8 h, and, if necessary, crystallizations will require a further 48 h.
authors.affiliation: School of Chemistry, Newcastle University, Newcastle upon Tyne, UK. simon.doherty@ncl.ac.uk
authors.forename: Simon
authors.initials: S
authors.lastname: Doherty
authors.forename: Catherine H
authors.initials: CH
authors.lastname: Smyth
authors.forename: Julian G
authors.initials: JG
authors.lastname: Knight
authors.forename: Stephen A K
authors.initials: SA
authors.lastname: Hashmi
mesh_terms: D000873:Anthracenes / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D002621:Chemistry / Q000379:methods; D056831:Coordination Complexes / Q000737:chemistry*; D006046:Gold / Q000737:chemistry; D015394:Molecular Structure; D010165:Palladium / Q000737:chemistry
chemical_list: C577499:11-dicyclohexylphosphino-12-phenyl-9,10-dihydro-9,10-ethenoanthracene; D000873:Anthracenes; D056831:Coordination Complexes; D010165:Palladium; D006046:Gold