Racemic t-butylphenylphosphine oxide was resolved via formation of diastereoisomeric complexes with (+)-(R)-1, 1′-binaphthalene-2, 2′-diol and (+)-(S)-mandelic acid. With the latter complexing agent, separation of the essentially enantiopure (−)-(S)-enantiomer was achieved in a single complexation process. Addition of paraformaldehyde to this enantiomer gave α-hydroxymethyl-t-butylphenylphosphine oxide with high stereoselectivity and ...