Unexpected Reaction of Secondary Phosphine Chalcogenides with Acridine

Secondary phosphine chalcogenides reacted with acridine under mild conditions according to the nucleophilic addition scheme to form 9-chalcogenophosphoryl-9,10-dihydroacridines.

     

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%.     

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.     

Quantum Chemical Study of the Addition of Secondary Phosphine Chalcogenides to Vinyl Selenides

Russian Journal of Organic Chemistry - DFT quantum chemical calculations at the B3PW91/6-31G(d) level of theory have shown that the addition of secondary phosphine sulfides and phosphine selenides...     

Copper-Catalyzed Coupling Reaction of Secondary Alkyl 2-Pyridinesulfonates with Alkyl Lithium-Based Reagents

The Cu(OTf)₂-catalyzed alkyl–alkyl coupling reaction of a secondary substrate MeCH(OSO₂Py)CH₂CH₂C₆H₄(4-OMe) with a nBuLi-based reagent prepared by transmetalation with MgBr₂ ⋅ THF₃ in THF produced a coupling product in 74 % yield. The use of soluble MgBr₂ ⋅ THF₃ in THF was required for this reaction. This method was applied to sBuLi and Ph(CH₂)₄Li. In contrast, transmetalation of MeLi with soluble MgCl₂ ⋅ THF₂ in THF produced the Me reagent, which was reactive for the coupling reaction. The reaction proceeded with inversion of the stereogenic carbon. Furthermore, (S)-14-methyloctadecan-2-one, a sex pheromone produced by lichen moths, was synthesized.     

Phosphorylation of Acetylaminophenols with Secondary Phosphine Chalcogenides: Synthesis of O-(Acetylamino)phenyl Chalcogenophosphinates

Russian Journal of General Chemistry - Oxidative cross-coupling of 4-acetylaminophenol (paracetamol) and its structural isomers (2- and 3-acetylaminophenols) with secondary phosphine chalcogenides...     

Regio- and Stereoselective Addition of Selenium Dichloride to Alkyl Propiolates

Russian Journal of Organic Chemistry - The reaction of selenium dichloride with methyl and ethyl propiolates leads to formation of anti-Markovnikov adducts. The regio- and stereoselective synthesis...     

Stereoselective Synthesis and Resolution of P-Chiral Phosphine Chalcogenides.

Abstract

New synthetic methods and resolution procedures securing ready access to the resolved P-chiral phosphinoylethenes, phosphinoylacetates and secondary phosphine oxides of diversified structures have been developed. The methods are based on processes employing stereoselective nucleophilic displacement at phosphorus, asymmetric deprotonation, immolative vinyl and chirality transfer from sulfur to phosphorus, chemical and enzymatic kinetic resolution, resolution via covalent diastereoisomers, as well as direct resolution of racemates by classical resolving agents and by chromatography on chiral stationary phases.     

One-Pot Synthesis of Substituted 4H-Chromenes by Three-Component Reaction of Alkyl Isocyanides,Dialkyl Acetylenedicarboxylates,and N-Aryl-3-hydroxynaphthalene-2-carboxamide

The reactive intermediate generated by the reaction of alkyl isocyanides and dialkyl acetylenedicarboxylates was trapped by N-aryl-3-hydroxynaphthalene-2-carboxamide for the preparation of substituted 4H-chromenes in good yields.      

Three-Component Reaction of Sulfonamides with Acetylene and Amines

Russian Journal of Organic Chemistry - N-(2-Phenyl-1-piperidin-1-ylethylidene)tosylamide was synthesized by oxidative coupling of arenesulfonamides, acetylenes, and secondary amines. The reaction...     

Three-Component Reaction of 1,3,4,6-Tetraketones with Acetone and Amines

Russian Journal of Organic Chemistry - 1,6-Diarylhexane-1,3,4,6-tetraones reacted with 2-aminophenol and acetone according to previously unknown pathway leading to the formation of...     

Reaction of tert‐Butyl Isocyanide with Alkyl Propiolates in the Presence of α‐Chloroketones

tert‐Butyl isocyanide reacts with α‐chloroketones in the presence of alkyl propiolates in one pot to afford functionalized γ‐iminolactones as sole product in good yields.     

Reaction of Alkyl Sulfoxides and Phenylphosphinic Acid with Amines. Alternative Reagents for Secondary Amines N-Alkylation

Phenylphosphinic acid and dialkylsulfoxides are found to be alternative reagents for respectively the reducing reagent (formic acid) and the alkylating reagent (aldehyde) currently used for secondary amines N-alkylation. Primary amines do not react with this system, but phenylglycine is decarboxilated to benzylamine.     

Three-Component Reaction of Dimedone with Aromatic Aldehydes and 5-Aminotetrazole

Russian Journal of General Chemistry - Reactions of dimedone with aromatic aldehyde and 5-aminotetrazole monohydrate proceeded with the formation of...     

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.     

Efficient Synthesis of 4-Phenyl-4H-pyran Derivatives via a DIPEA-catalyzed One-Pot Three-Component Reaction

Russian Journal of Organic Chemistry - A novel one-pot approach has been developed for a high-yield synthesis of 4-phenyl-4H-pyran derivatives by the three-component condensation of dimethyl...     

Three-Component Reaction of 1H-Pyrrole-2,3-diones with Malononitrile and Phthalhydrazide

Russian Journal of Organic Chemistry - Base-catalyzed three-component condensation of ethyl 4,5-dioxo-4,5-dihydro-1H-pyrrole-3-carbox­ylates with malononitrile and phthalhydrazide afforded...     

Three-Component,Four-Molecule,Ru-Catalyzed Cascade Reactions of Indoles and Alkyl Bromides with Sodium Nitrite

Abstract

An operationally simple domino approach for the ruthenium-catalyzed synthesis of (E)-2,3′-bi(3H-indol)-3-one O-alkyl oximes by the region- and stereoselective three-component, four-molecule reactions of indoles with sodium nitrite and alkyl bromides under mild reaction condition in dimethylformamide is described. Remarkably, multiple bonds including C?C, C=N, and C?O bonds were conveniently formed in one pot. The reaction is tolerant to air and is atom economical, in accordance with the concept of modern green chemistry.     

Reaction of Alkyl 2-Bromoalkanoates with Zinc and Arylglyoxales

Methyl 2-bromo-2-methylpropionate reacts with zinc and arylglyoxals under conditions of Reformatsky reaction in ether-HMPA mixture to afford 1-aryl-4,4,8,8-tetramethyl-2,6-dioxabicyclo[3.3.0]octane-3,7-diones in 68-85% yield. Methyl 2-bromopropionate reacts with zinc and 4-bromophenylglyoxal in the same way giving the bicyclic product in 28% yield. The bromination of 1-(4-tolyl)-4,4,8,8-tetramethyl-2,6-dioxabicyclo[3.3.0]octane-3,7-dione with bromosuccinimide results in successive replacement of hydrogens in the tolyl moiety by bromine. The calculation of formation enthalpy for stereoisomers of compounds obtained in AM1 approximation predicts the highest stability for chair-type conformation with eclipsed position of substituents at C¹ and C⁵ atoms.