A mild method for the facile removal of phosphine oxide from the crude products of Wittig and Appel reactions is described. Work-up with oxalyl chloride to generate insoluble chlorophosphonium salt (CPS) yields phosphorus-free products for a wide variety of these reactions. The CPS product can be further converted into phosphine.

Phosphine-catalyzed [2 + 4] annulation of allenoates with thiazolone-derived alkenes has been achieved under mild conditions, giving biologically important 6,7-dihydro-5H-pyrano[2,3-d]thiazole derivatives in high to excellent yields. With the use of Kwon's phosphine as the chiral catalyst, optically active products were obtained in good yields with excellent enantioselectivities.

Copper(I) halides are employed as ‘phosphine sponges’ to sequester phosphor-ylides when using phosphine-based Grubb’s metathesis catalysis in polar protic solvents and under heat. These cuprous halides are hypothesized to significantly slow the formation of the ruthenium hydride olefin isomerization catalyst. We demonstrate their use in both cross metathesis and ring-closing metathesis.

Solid-state NMR spectroscopy of selected phosphine oxides adsorbed on silica surfaces establishes the surface mobilities, even of phosphine oxides with high melting points. Crystal structures of the adducts Ph3 PO⋅HOSiPh3 and Cy3 PO⋅H2 O indicate that the interactions with silica involve hydrogen bonding of the P=O group to adsorbed water and surface silanol groups.

Organosilanes bearing a phosphine imide moiety were synthesized and crystallographically characterized. Reaction of the pentacoordinated hydrodiphenylsilyl derivative with water gave [2-(diphenylphosphino)phenyl]diphenylsilanol accompanied by both reduction of the phosphine imide moiety and hydrolytic oxidation of the Si-H moiety.

The regiodivergent palladium-catalyzed C-H arylation of pyrazolo[1,5-a]pyrimidine has been achieved, wherein the switch in regioselectivity between positions C3 and C7 is under complete catalyst control. A phosphine-containing palladium catalyst promotes the direct arylation at the most acidic position (C7), whereas a phosphine-free catalyst targets the most electron-rich position (C3).

A convenient and efficient phosphine-catalyzed sequential annulation domino reaction between dienic sulfones and MBH carbonates has been developed. In the presence of 20 mol% of tris(4-fluorophenyl)phosphine, functionalized bicyclo[4.1.0]heptenes were prepared in excellent yields and stereoselectivities under mild conditions.

Herein an efficient and direct copper-catalyzed coupling of oxazoline-containing aryl bromides with electron-deficient secondary phosphine oxides is reported. The resulting tertiary phosphine oxides can be reduced to prepare a range of PHOX ligands. The presented strategy is a useful alternative to known methods for constructing PHOX derivatives.

The stoichiometric reaction of trityl cation with two equivalents of Ph2PH affords the phosphine stabilized phosphenium salt [Ph2(H)PPPh2][B(C6F5)4] via hydride abstraction, while catalytic amounts of B(p-HC6F4)3 effects catalytic phosphine dehydrocoupling with the liberation of H2. This reaction is accelerated by the presence of olefin or imine, effecting concurrent hydrogenation.

N-Diphenylphosphino-7-aza-benzobicyclo[2.2.1]hept-2-ene (2) behaves as a chelating phosphine-alkene ligand for Pd(0) and Pd(II), promoting direct alkyl-alkyl and indirect alkyl-halide reductive elimination reactions due to the stabilisation of the resulting bis(phosphine-alkene)Pd(0) complex.