The novel P-chirogenic anisylphenylMOP derivatives (R,R) and (R,S)-2-(anisylphenylphosphino)-2'-methoxy-1, 1'-binaphthyl (10a and b) have been synthesized and their corresponding oxides characterised by X-ray crystallography. The results of a parallel screening regimen with various reducing agents highlight the sensitivity of the tertiary phosphine oxides to epimerisation and, interestingly. reveal that the P=O, O-CH3 and P-C6H5 bonds can all be cleaved selectively depending on the reducing agents employed. An alternative synthesis was provided by direct coupling of the secondary phosphine with (R)-methoxytriflate 4, which led to the isolation of the optically pure P-chirogenic phosphines via their borane adducts. A brief study of the coordination chemistry of 10a with different rhodium precursors, relevant to the catalytic asymmetric addition of boronic acids to aldehydes is also reported. (C) 2004 Elsevier B.V. All rights reserved..