Asymmetric Synthesis ofP‐Chirogenic Phosphorus Compounds

Abstract

P-chiral phosphorus compounds are used in many areas of chemistry including biologically active pharmaceuticals, agrochemicals, and ligands for transition metal complexes. This chapter points out significant advances in the asymmetric synthesis of P-chiral organophosphorus compounds with many applications in stereoselective synthesis and asymmetric catalysis. It describes asymmetric addition and cycloaddition reactions, reductions and oxidation, including metal-catalyzed and non-metal biocatalytic methods, in addition to synthetic approaches via nucleophilic substitution of appropriately substituted precursors. Tetracoordinate organophosphorus compounds exhibit, in general, high configurational stability, although this depends on the structure of the compounds. Tertiary phosphine oxides are the most stable, esters of chiral phosphorus acids are also configurationally stable, although they racemize slowly upon heating. Nucleophilic substitution reactions at the tetracoordinate pentacovalent phosphorus atom are often highly stereoselective occurring with essentially complete inversion or retention of configuration. Pentacoordinated phosphorus compounds have attracted attention as models of the transition state (TS) in nonenzymatic and enzymatic phosphoryl transfer reactions.