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The synthesis of phosphorus molecules presenting a chiral center on the P‐atom, also known as P‐stereogenic compounds, has long attracted the curiosity of the scientific community. Indeed, these chemical compounds feature many peculiar properties, allowing their use in various fields of applications, ranging from medicine to enantioselective catalysis. However, their synthesis, and more particularly the introduction and retention of the chiral information on the phosphorus center, remains a very challenging task. That is why this review article focuses on the recent advances in the enantioselective synthesis of P‐stereogenic molecules, with a particular focus on the introduction of the chiral center on the phosphorus atom. This article summarizes the main synthetic approaches directed towards the enantioselective synthesis of such chemical entities with a historical perspective. Thus, approaches based on the use of chiral auxiliaries attached to the phosphorus atom and the use of chiral stoichiometric reagents will be discussed first, as they were historically the first to be developed. Then, the recent discoveries in the catalytic and enantioselective synthesis and the direct optical resolution of P‐chiral compounds will be discussed. [ABSTRACT FROM AUTHOR]

Verkade's superbases, entrapped in the cavity of enantiopure hemicryptophane cages, have been synthesized with enantiomeric excess (ee) superior to 98%. Their absolute configuration has been determined by using electronic circular dichroism (ECD) spectroscopy. These enantiopure encaged superbases turned out to be efficient chiral derivatizing agents for chiral azides, underlining that the chirality of the cycloveratrylene (CTV) macrocycle induces different magnetic and chemical environments around the phosphazide functions. [ABSTRACT FROM AUTHOR]

We present recent advances in the understanding of the reduction of optically pure hydroxyalkylphosphinates and phosphine oxides, which represent key intermediates for the preparation of P-stereogenic ligands. Their reduction leads to P-chiral phosphinites and phosphines, respectively, and occurs stereospecifically with inversion of configuration using BH3·THF, which plays three roles: activating, reducing and protecting agent. The formation of by-products as hydroxyalkyl secondary phosphine-boranes has also been studied. [ABSTRACT FROM AUTHOR]

In this paper we describe the synthesis of functionalised mesoporous organosilicas containing a mannitol derivative in the framework. For this purpose, a bis-silylated precursor 3,4-Di-O-[3-(triethoxysilylpropyl)carbamate]-1,2:5,6-di-O-isopropylidene-D-mannitol was prepared by coupling of 1,2:5,6-di-O-isopropylidene-D-mannitol with 3-(triethoxysilylpropyl)isocyanate. The framework-functionalised materials were obtained in one step by the “direct synthesis” method which consists of a co-hydrolysis and polycondensation of a bis-silylated mannitol precursor with tetraethylorthosilicate (TEOS) in the presence of a non-ionic triblock co-polymer (P123) as structure-directing agent. Interestingly, deprotection of the 1,2,5,6 OH functional groups occurred during the material synthesis. The obtained solids were characterized by 13C and 29Si CP-MAS NMR, N2adsorption-desorption, powder X-ray diffraction, TEM and elemental analysis. We have shown that, the OH functional groups, which are released during the synthesis of the mesoporous silica, can be used for chelation of ions and stabilisation of nanoparticles. The subsequent growth of gold (0) nanoparticles in the wall has been investigated and evidenced. [ABSTRACT FROM AUTHOR]