N. A. Belogorlova

Addition of secondary phosphines to N-vinylpyrroles

Abstract Secondary phosphines 1 – 3 react readily with N -vinylpyrroles 4 and 5 under radical initiation to give regiospecifically anti-Markovnikov adducts, diorganyl-2-(1-pyrrolyl)ethylphosphines 6a – d , highly reactive building blocks for organic synthesis, in 88–91% yields.

Reactions of Elemental Phosphorus and Phosphine with Electrophiles in Superbasic Systems: XIV.1 Phosphorylation of 2-Vinylnaphthalene with Elemental Phosphorus and Phosphines in the KOH-DMSO System

Elemental phosphorus (red or white) reacts with 2-vinylnaphthalene while heating at 90-96°C in the superbasic KOH-DMSO system to form 2-(2-naphthyl)ethylphosphine, 2-(2-naphthyl)ethylphosphinic acid, bis[2-(2-naphthyl)ethyl]phosphine, bis[2-(2-naphthyl)ethyl]phosphine oxide, and tris[2-(2-naphthyl)ethyl]phosphine oxide in a total yield of up to 40%. Selective conditions for preparing the tertiary phosphine oxide from white phosphorus and 2-vinylnaphthalene in 58% yield were found. Phosphine and (2-phenylpropyl)phosphine add to 2-vinylnaphthalene in the KOH-DMSO system to form, under certain conditions, corresponding secondary phosphines in high yields.

Superbase-Assisted Addition of Phosphine to 1-Methoxy-4-vinylbenzene: Toward a Rare Family of Organic Phosphines

Abstract Phosphine reacts with 1-methoxy-4-vinylbenzene in the superbase suspension KOH-dimethylsulfoxide (70–100 °C, atmospheric pressure) to form regiospecifically anti-Markovnikov adducts, bis[2-(4-methoxyphenyl)ethyl]phosphine (1) and tris[2-(4-methoxyphenyl)ethyl]phosphine (2), representatives of rare arylalkylphosphines. The conditions for the selective preparation of phosphines 1 or 2 in 67% and 80% yields, respectively, have been elaborated. The phosphines have been oxidized with aqueous solution of H2O2, elemental sulfur, or selenium to afford the corresponding phosphine chalcogenides in good yields (95–99%). GRAPHICAL ABSTRACT

First example of the \( C_{sp^2 } \)-P bond formation in the reaction of red phosphorus with hetaryl halides

Direct reactions of red and white phosphorus with electrophiles (aryland hetarylalkenes, arylacetylenes, alkyl, allyl, and benzyl halides) in superbasic systems alkali metal hydroxide – dipolar aprotic solvent (DMSO, HMPTA) or under the conditions of phase transfer catalysis are now considered as a novel chlorine-free method of formation of the С–P bond [1, 2]. Within this approach, the one-pot methods have been elaborated for the synthesis of various phosphines, phosphine oxides, and phospinic acids [1, 2] which had earlier been obtained by multistep processes from phosphorus halides. However, in the case of the substitution reaction only the Сsp3–P bond was formed. Recently, tris(1-naphthyl)phosphine was synthesized from red phosphorus and 1-naphthyl bromide in the system KОН–DMSO [3]. To the best of our knowledge, there are no data in the literature on the formation of the Сsp2–P in the reactions of elemental phosphorus with hetaryl halides in superbasic systems.

Synthesis of [2-(methoxyaryl)-1-methylethyl]phosphinic acids from red phosphorus and (allyl)(methoxy)benzenes

Abstract(Allyl)(methoxy)benzenes react with red phosphorus in the superbasic system KOH-DMSO in the presence of small amounts of water and hydroquinone (3 h, 130 °C) to regio- and chemoselectively give [2-(methoxyaryl)-1-methylethyl]phosphinic acids in preparative yields up to 52%. The reactions involve isomerization of allylbenzenes into (prop-1-enyl)benzenes.

Synthesis of tris(2-pyridyl)phosphine from red phosphorus and 2-bromopyridine in the CsF-NaOH-DMSO superbasic system

164 Pyridylphosphines are widely used as polydentate chemolabile P,N ligands for the design of multipur pose metal complex catalysts [1–3], highly reactive building blocks in organic synthesis [4], and precur sors in the preparation of new pharmaceuticals [5, 6]. Among pyridylphosphines, tris(2 pyridyl)phosphine is of special interest as a tripodal ligand of chelating type due to the geminal arrangement of the nitrogen atoms with respect to the phosphorus atom. Metal complexes obtained from tris(2 pyridyl)phosphine are efficient catalysts for industrially important processes, such as alkene hydroformylation [7], ethylene poly merization [8], methoxycarbonylation of acetylenes [9], and diene synthesis [10].

Novel quinine, lupinine, and anabasine derivatives containing dithiophosphinate groups

A three-component, atom-economic reaction between natural quinine, lupinine, or anabasine, secondary phosphines, and elemental sulfur occurs under mild conditions to yield previously unknown optically active dithiophosphinates.

Phosphorylation of Allyl Halides with White Phosphorus

White phosphorus reacts with allyl bromide in the system KOH-dioxane-H 2 O at room temperature to form tris(propen-2-yl), bis(propen-2-yl)(E-propen-1-yl), and bis(E-propen-1-yl)(propen-2-yl)phosphine oxides in a total quantitative yield, their molar ratio being 1:0.5:0.1.

One-Pot Vinylation of Secondary Phosphine Chalcogenides with Vinyl Sulfoxides

A facile, one-pot vinylation of secondary phosphine chalcogenides with alkyl(or aryl) vinyl sulfoxides has been elaborated. The vinylation comprises the nucleophilic addition of secondary phosphine chalcogenides to the vinyl sulfoxides (∼50 mol% KOH, dioxane, 25–40°C, 1 h) followed by the elimination of sulfenic acids from the adducts (additional equivalent of KOH, 60–70°C, 1.5–2.0 h), the yields of target tertiary vinyl phosphine chalcogenides reaching 92%.

Microwave synthesis of secondary phosphines and phosphine oxides from red phosphorus and allyl(methoxy)benzenes in KOH-DMSO

Bis[1-(methoxyphenyl)propan-2-yl]phosphines and bis[1-(methoxyphenyl)propan-2-yl]phosphine oxides were synthesized by phosphorylation of allyl(methoxy)benzenes in the system red phosphorus-KOH · 0.5 H2O-DMSO under microwave irradiation.