Ortho-lithiation of (2
R,4
S,5
R)-3,4-dimethyl-2-ferrocenyl-5-p
henyl[1,3,2]oxazaphospholidine 2-oxide
2 was carried out with diastereoselectivityof >99%, affording a new and efficient way for introducing planar chirality into t
he ferrocene backbone. Various electrophiles were used toquench t
he lithiated species, showing t
he wide applicability of t
he new
ortho-directing group and its potential to generate ligands for use inasymmetric catalysis.