Tertiary Phosphine Oxides in Reaction with Benzaldehyde

Symmetrical and unsymmetrical tertiary phosphine oxides containing benzyl and 5-chloro-2-thienyl radicals stereoselectively react with benzaldehyde in the sodium amide-THF system to form the E isomers of 1-organyl-2-phenylethene and diorganylphosphinic acids in high yields. Triethyl, tris(2-phenyl- ethyl)-, and tris[(4-methoxyphenyl)methyl]phosphine oxides under the above-mentioned conditions do not react with benzaldehyde.     

Reaction of Tribenzylphosphine Oxide with Aldehydes

Tribenzylphosphine oxide readily and stereoselectively reacts with aliphatic, aromatic, and heteroaromatic aldehydes in the presence of strong bases yielding exclusively (or predominantly) E-isomers of 1-organyl-2-phenylethenes and dibenzylphosphinic acid.     

Facile Exchange of Phosphoryl Oxygen by Sulfur and Selenium in Teriary Phosphine Oxides

Russian Journal of General Chemistry -     

Antiviral drug nevirapine as a template for hydrated imidazoline ring expansion (HIRE): Rapid access to the diarene-fused 1,4,7-triazecine ring system

The tricyclic ring system of the antiviral drug nevirapine has been employed to test the workability of the hydrated imidazoline ring expansion (HIRE) reaction which was previously exemplified for [1.4]oxazepine and [1.4]thiazepine counterparts. The imidazoline nucleus was grafted onto the lactam moiety of nevirapine in two high-yielding steps. Subsequent N-alkylation and the HIRE reaction proceeded as envisioned and delivered rare ring-expanded diarene-fused 1,4,7-triazecines with a diversity of alkyl substituents at the lactam nitrogen atom. These findings extend the scope of the HIRE reaction to the medicinally prominent [1.4]diazepine chemical space.     

Reaction of Secondary Phosphine Oxides with Aromatic Aldehydes

Nucleophilic addition of secondary phosphine oxides to aromatic aldehydes proceeds under mild conditions (20-60°C, 10-40 h) and provides [bis(2-organylethyl)](arylhydroxymethyl)phosphine oxides in high yields.     

Synthesis and Properties of 2-(Diorganylphosphorylhydroxymethyl)-1-organylimidazoles

1-Organyl-2-formylimidazoles and -benzimidazoles react with diorganylphosphine oxides under mild conditions (room temperature, dioxane, 1 h) to give in practically quantitative yields 2-(diorganylphosphorylhydroxymethyl)-1-organylimidazoles - highly reactive synthons and polydentate ligands for the design of metal complex catalysts.     

Hydrogen Bonds in 2-(Diorganylphosphorylhydroxymethyl)-1-organylimidazoles

Structures of 2-(diorganylphosphorylhydroxymethyl)-1-organylimidazoles were studied by IR and ¹H and ^{3 1}P NMR spectroscopy, and also by ab initio calculations (HF/6-31G*). Formation of intramolecular O-H+++O = P hydrogen bonds in solutions of these compounds in CCl₄ and CHCl₃ was established.