Applications and stereoselective syntheses of P-chirogenic phosphorus compounds

Abstract

Phosphorus compounds bearing chirality on the P-center are usually qualified as P-chirogenic or P-stereogenic. This chemical class concerns natural products, agrochemistry, molecular materials, biology and pharmacy, although it is certainly in coordination chemistry and in asymmetric catalysis using chiral transition metal complexes that P-chirogenic phosphorus compounds are the most used. The chiral phosphine ligands and their uses in asymmetric metal-catalyzed reactions have been widely reviewed in literature. However, an overview covering the applications as well as the stereoselective syntheses of all classes of phosphorus compounds has not yet been provided. This review reports the best stereoselective or asymmetric syntheses, the most efficient P*-building blocks and functionalisation of P-chirogenic compounds, in the light of chiral phosphorus compound applications. It is an extensive and useful documentation from pioneering work to recent advances in phosphorus stereochemistry.

NHC‐Catalyzed Metathesis and Phosphorylation Reactions of Disulfides: Development and Mechanistic Insights

“…High‐level ab initio studies were carried out to propose plausible mechanisms for these reactions. This work opens up new possibilities in NHC‐mediated organic synthesis, as the catalytic activity of NHCs on organosulfur and organophosphorus substrates has been inadequately studied …”

Pd-catalyzed enantioselective C–H arylation of phosphinamides with boronic acids for the synthesis of P-stereogenic compounds

“…1 Most importantly, they are 'privileged' ligands [2][3][4][5][6] or organocatalysts 5,[7][8][9][10][11][12] in catalytic asymmetric synthesis. However, conventional studies have concentrated overwhelmingly on planar, axial, and C-centered derivatives.…”

The resolution of acyclic P‐stereogenic phosphine oxides via the formation of diastereomeric complexes: A case study on ethyl‐(2‐methylphenyl)‐phenylphosphine oxide

“…3,4 Moreover, a number of deoxygenation or deboronation protocols were developed for the preparation of the corresponding P(III) compounds, and the stereochemical outcome of those reactions was also studied in detail. [7][8][9] In those reactions, (−)-menthol and (−)-ephedrine are frequently used chiral templates, 6,10-17 but other synthetic derivatives were also used. [7][8][9] In those reactions, (−)-menthol and (−)-ephedrine are frequently used chiral templates, 6,10-17 but other synthetic derivatives were also used.…”