The review describes preparation of P,N-bidentate ligands without a P–N bond and their use in asymmetric catalysis. Diverse
types of aminophosphines are considered with emphasis on P,N-ferrocene ligands, phosphino-oxazolines and phosphinopyridines. The
following major synthetic approaches to aminophosphines and related compounds are summarized: (i) via lithiation, (ii) the use of Grignard
reagents, (iii) nucleophilic substitution using metal phosphides, (iv) Staudinger method, (v) hydrophosphination of α,β-unsaturated
carbonyl compounds, (vi) Cu- and Pd-catalyzed C–P bond formation reactions, and (vii) reactions of cyclopalladated complexes with
metal phosphides and HPPh2. Highlights of aminophosphine applications in asymmetric synthesis include their use in hydrogenation, hydrosilylation,
and hydroboration reactions as well as in various transformations leading to a C–C bond formation such as Suzuki coupling,
Meerwein-Eschenmoser-Claisen rearrangement, Mukaiyama aldol reaction, Tsuji allylation and ethylene oligomerization.