SYNTHESIS AND CHEMISTRY OF A NEW P-N CHELATING LIGAND - 6-(2'-DIPHENYLPHOSPHINO-1'-NAPHTHYL)PHENANTHRIDINE AND 6-(2'-DIPHENYLPHOSPHINO-1'-NAPHTHYL)PHENANTHRIDINE

A synthesis of the title phosphinamine (PHENAP) is described, followin g previously established methodology, Resolution via the C,N-palladocy cle derived from (R)-N,N-dimethyl-alpha-methyl-1-naphthylamine led to two crystallographically defined complexes with the (R,S)-form posessi ng a chelated ligand and the (R,R)-form open with only the phosphine c oordinated. Palladium allyl complexes of the ligand were strikingly di fferent from those of the corresponding isoquinoline ligand QUINAP, an d the differences could be rationalised by recourse to molecular model s, with the additional fused arene ring of PHENAP playing a critical p art in defining the coordination sphere through its steric pressure, A brief appraisal of Pd-catalysed allylic alkylation reactions was perf ormed with the new ligand.