Asymmetric Electrophilic Reactions in Phosphorus Chemistry

Abstract

This review is devoted to the theoretic and synthetic aspects of asymmetric electrophilic substitution reactions at the stereogenic phosphorus center. The stereochemistry and mechanisms of electrophilic reactions are discussed—the substitution, addition and addition-elimination of many important reactions. The reactions of bimolecular electrophilic substitution SE2(P) proceed stereospecifically with the retention of absolute configuration at the phosphorus center, in contrast to the reactions of bimolecular nucleophilic substitution SN2(P), proceeding with inversion of absolute configuration. This conclusion was made based on stereochemical analysis of a wide range of trivalent phosphorus reactions with typical electrophiles and investigation of examples of a sizeable number of diverse compounds. The combination of stereospecific electrophilic reactions and stereoselective nucleophilic reactions is useful and promising for the further development of organophosphorus chemistry. The study of phosphoryl group transfer reactions is important for biological and molecular chemistry, as well as in studying mechanisms of chemical processes involving organophosphorus compounds. New versions of asymmetric electrophilic reactions applicable for the synthesis of enantiopure P-chiral secondary and tertiary phosphines are discussed.

Exploring the Reactivity of Substituted [(Allyloxy)methyl]phosphonates in Cycloaddition and Coupling Reactions

“…Organophosphorus compounds, particularly those with a phosphonate or phosphonic acid group, have considerable potential for a variety of applications in industrial, agricultural, and medicinal chemistry. 1 2 3 4 5 In a recent paper, we described the synthesis of β-functionalized [(allyloxy)methyl]phosphonates 1 (Scheme 1 ), and studied their reactivity towards various nucleophiles such as amines or thiols to prepare linear original phosphonate compounds. 6…”

Enzymatic Desymmetrisation of Prochiral Phosphines and Phosphine P-Sulfides as a Route to P-Chiral Catalysts

“…The absolute configuration of the newly obtained enantiomerically enriched monoacetates was determined as follows: phosphine 14 (Table 1, entry 4) was oxidized with air to give phosphine oxide (-)-(R)-5, whose absolute configuration and optical rotation are known from our previous work [8]. Since oxidation with air proceeds with the retention of the configuration at phosphorus [15], (S) configuration was ascribed to (-)-phosphine 14 obtained. In turn, the reaction of 14 with elemental sulfur, proceeding also with retention of configuration at phosphorus [15], gave phosphine sulfide 24.…”

“…Since oxidation with air proceeds with the retention of the configuration at phosphorus [15], (S) configuration was ascribed to (-)-phosphine 14 obtained. In turn, the reaction of 14 with elemental sulfur, proceeding also with retention of configuration at phosphorus [15], gave phosphine sulfide 24. Hence, the absolute configuration of the latter is (+)-(R) (Scheme 7), that is, the same as the one obtained in the enzymatic desymmetrisation.…”

Phosphorus Compounds of Natural Origin: Prebiotic, Stereochemistry, Application

“…Consequently, it cannot be registered in aqueous solutions because of the insignificant lifetime under these conditions. However, metaphosphate can be detected in highly polar and weakly nucleophilic nonaqueous media [46][47][48][49][50]. In addition, the metaphosphate anion PO 3 − exists in a stable form in the gas phase and has been recorded by various physical methods.…”