Some new approaches for asymmetric synthesis of chiral ferrocenyl liga
nds are described. Many types of ferrocene compounds with planar chira
lity were prepared through diastereoselective ortholithiation, thanks
to a chiral sulfoxide or chiral acetal auxiliary. Various mono- and di
phosphines may be subsequently generated. In the sulfoxide route, a ke
y intermediate is pure monolithioferrocene. A convenient procedure was
set up, involving the isolation of stable tri-n-butylstannyl-ferrocen
e as a precursor of monolithioferrocene. The species Fc(2)PH (Fc = fer
rocenyl) and its borane protected derivative allowed to synthesize chi
ral diphosphines where the usual PPh(2) groups are replaced by the PFc
(2) fragment.