Damien Hérault

H-Adamantylphosphinates as Universal Precursors of P-Stereogenic Compounds

A new family of H-adamantylphosphinates as universal precursors of P-stereogenic ligands was obtained in one step from commercial chlorophosphines. Both enantiomers of these air- and moisture-stable intermediates can easily be separated by semipreparative chiral HPLC on a gram scale and individually undergo stereoselective transformations to afford each enantiomer of a set of P-stereogenic compounds such as secondary phosphine oxides and boron-protected monophosphines.

Stereospecific Synthesis of α- and β-Hydroxyalkyl P-Stereogenic Phosphine–Boranes and Functionalized derivatives: Evidence of the PO Activation in the BH3-Mediated Reduction

Access to hydroxy-functionalized P-chiral phosphine-boranes has become an important field in the synthesis of P-stereogenic compounds used as ligands in asymmetric catalysis. A family of optically pure α and β-hydroxyalkyl tertiary phosphine-boranes has been prepared by using a three-step procedure from readily accessible enantiopure adamantylphosphinate, obtained by semi-preparative HPLC on multigram scale. Firstly, a two-step one-pot transformation affords the enantiopure hydroxyalkyl tertiary phosphine oxides in good yields and enantioselectivities. The third step, BH3 -mediated reduction, allows the formation of the desired phosphine-boranes with excellent stereospecifity. The mechanistic study of this reduction provides new evidence to elucidate the crucial role of the pendant hydroxy group and the subsequent activation of the P=O bond by the boron atom.

The Hydroxyalkyl Moiety As a Protecting Group for the Stereospecific Alkylation of Masked Secondary Phosphine-Boranes.

The synthesis of functionalized tertiary phosphine-boranes has been developed via a chemodivergent approach from readily accessible (hydroxymethyl) phosphine-boranes under mild conditions. O-Alkylation or decarbonylative P-alkylation product could be exclusively obtained. The P-alkylation reaction was found to proceed in moderate to very good yields and very high enantiospecificity (es >95%) using a variety of alkyl halides as electrophiles. The configurational stability of the sodium phosphido-borane intermediate was also investigated and allowed a deeper understanding of the reaction mechanism, furnishing secondary phosphine-boranes in moderate yield and enantiopurity.

Mechanistic aspects of the stereospecific reduction of chiral hydroxyalkyl phosphinates and phosphine oxides

Abstract 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.

Comparison of two soft chemistry routes for the synthesis of mesoporous carbon/β-SiC nanocomposites

We compare the influence of using either molecular or colloidal precursors on the synthesis of a ceramic material containing SiC and porous carbon. Remarkably, the temperature of synthesis for crystalline SiC is independent of the route chosen. The excess carbon in the initial mixture is the source of the excess porous carbon that binds to the crystalline domains of SiC in the final products. Interestingly, increasing the initial area of surface contact between carbon and silicon in the ceramic precursor results in different porosities in the ‘meso’ range. Simultaneous control of the size and the relative amounts of Si and C in the precursors allows control to be exerted over the nature and texture of the final powders. A simple and general mechanism is herein proposed to explain the evolution of the surface area as a function of the volume fraction of residual carbon in the synthesised ceramic.