Chiral Bidentate Heterodonor P-P’ ligands

The synthesis, structure, and catalytic applications of several groups of chiral heterodonor P–P’ ligands (asymmetric diphosphines, phosphine-aminophosphines, phosphine-phosphoramidites, phosphine-phosphinites, phosphine-phosphonites, and phosphine-phosphites) are presented in this chapter. In addition, a brief discussion of the electronic properties of the P(III) coordinating fragments of these ligands is included. A common feature of P–P’ ligands is their highly modular structure, which allows precise catalyst optimization, leading to outstanding control of enantioselectivity. The range of catalytic reactions covered includes a wide variety of Rh and Ir asymmetric hydrogenation reactions, olefin hydroformylation, different types of couplings, hydrocyanations, or addition of Grignard reagents, among others. In each type of transformation, greater attention is paid in this chapter to challenging goals, rather than to the performance of catalysts on benchmark substrates. However, representative cases and literature references for the latter have also been provided.