P-Chirogenic Benzo-Fused Phenoxaphosphane: Synthesis, Resolution and Study of the Stereochemical Properties of the Corresponding Palladium Complexes

The synthesis and resolution of chiral phenoxaphosphane 3, with the stereogenic center at the phosphorus atom, is described. Compound 3 has been synthesized following a well‐known procedure for trapping a phosphorus atom within a six‐membered ring. The resolution of the racemic mixture of 3 was achieved through separation of its diastereomeric palladacycle derivatives 7a,b and 9a,b. The absolute configuration of enantiopure phosphanes 3a,b was assigned unequivocally by means of X‐ray crystal structure determination for complex 9a and by combination of NOE(1H–1H)/COSY(1H,1H) spectroscopy and DFT calculations for complexes 7a,b, which in both cases led to identical results. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) Phenoxaphosphane 3, a chiral cyclic analogue of triphenylphosphane, has been synthesized and resolved in its two enantiomeric forms. The stereochemical properties of the corresponding palladium complexes have been extensively studied, both at the solid state and in solution.