Totally diastereoselective synthesis of new P-chirogenic o-trimethylsiloxyaryl diazaphospholidines and o-hydroxyaryl diazaphospholidine–borane complexes

Synthesis and Characterization of the Trihalophosphine Compounds of Ruthenium [RuX2(η6-cymene)(PY3)] (X = Cl, Br, Y = F, Cl, Br) and the Related PF2(NMe2) and P(NMe2)3Compounds; Multinuclear NMR Spectroscopy and the X-ray Single Crystal Structures of [RuBr2(η6-cymene)(PF3)], [RuBr2(η6-cymene)(PF2{NMe2})], and [RuI2(η6-cymene)(P{NMeBoshaala1, Simpson2, Autschbach3 et al. 2008Inorg. Chem.142120View full textAdd to dashboardCite

“…The high-frequency positive convention was followed for 19 Phosphorus trichloride, phosphorus tribromide, and tris(dimethylamino)phosphine were obtained from Aldrich and transferred to Rotaflo ampoules for storage under nitrogen. Dichloro(dimethylamino)phosphine was prepared by a literature method 71 and converted to difluoro(dimethylamino)phosphine by treatment with antimony trifluoride in the absence of solvent. 72,73 Trifluorophosphine (0.01-0.02 mol) was prepared by dropwise addition of PBr 3 to excess powdered SbF 3 ; the use of a nitrogen gas sweep, entrainment through two traps (-78 °C), and collection at -196 °C produced a pure product ( 31 P and 19 F NMR analysis).…”

Diastereoselective Synthesis of New P‐Stereogenic (ortho‐Hydroxyaryl)diazaphospholidine–Borane Complexes by a Totally Stereoselective P–O to P–C Migration Rearrangement

“…Column chromatography was performed on SDS silica gel (70-230 mesh). 1 H and 13 C NMR spectra were recorded in CDCl 3 solution at 200.00 and 50.30 MHz with a Bruker AC200 spectrometer. 31 P NMR spectra were recorded in CDCl 3 solution at 40.50 MHz with a Bruker AC100 spectrometer (the usual abbreviations are used: s, singlet; d, doublet; t, triplet; q, quadruplet; m, multiplet).…”

“…[13] These complexes are the protected forms of ortho-phosphanylphenols, [14] which are ambident molecules with two different nucleophilic sites, a hard oxygen atom and a soft phosphorus atom. Because they can react at oxygen or phosphorus or at both nucleophilic sites and also because their electronic and steric properties can easily be modulated by varying the substituents on the phosphorus atom and on the aromatic ring, they are of great interest in catalysis [15] and in complex chemistry.…”

“…[18] On the basis of these results, we have recently reported a totally diastereoselective synthesis of (ortho-hydroxyaryl)diazaphospholidines, in the form of their borane complexes (Scheme 1). [13] Unless this approach represents the first accurate and totally diastereoselective method for the preparation of P-stereogenic 2-hydroxyarylphosphane ligands, it suffers from several limitations. For example, overall yields are quite good but not excellent, and the choice of the chiral auxiliary is limited to diamines.…”

“…Totally diastereoselective synthesis of (ortho-hydroxyaryl)diazaphospholidine-borane complexes. [13] Scheme 2. Intramolecular 1,3-carbanionic rearrangement of orthometallated phenoxyphosphorus compounds.…”