Recent advances in synthesis of P-BH3 compounds.

This chapter is dedicated to the main achievements since 2007 regarding the synthesis of BH3-phosphorus complexes. Among this class of compounds, phosphine-boranes are the most studied derivatives, mainly as valuable surrogates of phosphines, enabling easy handling and purification. In contrast, metal phosphido-boranes have so far only been considered as in situ intermediates in the P-functionalization of secondary phosphine-boranes. Thorough investigations of their structures as well as their chemical properties have recently been reported. Besides phosphine-boranes and their phosphides, new families of phosphorus-BH3 complexes, have emerged as useful precursors of new structures in the asymmetric series. New routes toward optically active phosphinous-acid boranes and their esters were developed and applied to the synthesis of enantiopure P-stereogenic secondary and tertiary phosphine-boranes. The stereoselective synthesis of P-stereogenic aminophosphine-boranes, precursors of a new class of chiral ligands, has been reported. Studies dealing with the synthesis and reactivity of phosphonite-boranes were successfully applied to the development of efficient syntheses of functionalized H-phosphinates, compounds difficult to access by other routes.