Synthesis of a selective estrogen receptor β-modulator via asymmetric phase-transfer catalysis

An efficient asymmetric synthesis of selective estrogen receptor β-modulator (S)-4-bromo-9a-butyl-8-chloro-6-fluoro-7-hydroxy-1,2,9,9a-tetrahydro-fluoren-3-one was developed. The route features a chemoselective aromatic chlorination reaction, an asymmetric phase-transfer-catalyzed alkylation of an indanone with efficient ee upgrade by racemate crystallization, and a robust bromination reaction using imidazole as an in situ bromine trap to avoid overreaction. The synthesis proceeds in 34% yield over 8 steps from 2-fluoroanisole, and provides material with >99.5% ee.     

How iodide anions inhibit the phase-transfer catalyzed reactions of carbanions

The inhibitory effect of iodide anions on the phase-transfer catalyzed reactions of carbanions generated in liquid-liquid two-phase systems by aqueous NaOH is due to preferential location of these anions in the interfacial region of the two-phase system—organic phase/concd aqueous NaOH. In such situation, the basic activity of NaOH in this region is decreased and the equilibrium of deprotonation of the carbanion precursors is disfavoured.     

A new type of phase-transfer catalysis via continuous transfer of fluoride anions to the organic phase in the form of potassium difluorotriphenylstannate

Fluorination of alkyl halides and sulfonates is efficiently executed in a liquid-solid phase-transfer catalysis system with Ph₃SnF as phase-transfer catalyst acting via continuous formation of lipophilic Ph₃SnF₂ anions entering the organic phase in the form of the potassium salt.     

Ionic liquids as efficient phase-transfer catalysts for the solid base-promoted monoalkylation of diethyl malonate

Ionic liquids （ILs） based on 1,3-dialkylimidazolium and tetraalkylammonium cations were employed as a series of efficient, environmentally benign phase-transfer catalysts （PTCs） for the base-promoted monoalkylation of diethyl malonate. The influence of various heterogeneous bases on yields was studied. Good yields and high selectivity were obtained. Solvent-free, mild reaction condition, short reaction time, and easy purification were the merits of this method. The catalytic system （IL-hase） could also be recycled after the extraction of products with ether.     

Catalytic oxidation of organic substrates with hydrogen peroxide in two-phase systems in the presence of peroxo-polyoxotungstates containing organic ligands

The prospects of using bifunctional homogeneous metal-complex catalysts based on peroxo-polyoxotungstates with organic ligands (tertiary phosphine oxides) were exemplified by oxidation of benzyl alcohol and cyclooctene with hydrogen peroxide in two-phase systems (organic phase — liquid phase).     

Cocatalysis in phase-transfer catalyzed fluorination of alkyl halides and sulfonates

Phase-transfer catalyzed (PTC) fluorination of alkyl halides and sulfonates with solid KF proceeds efficiently when cocatalyst triphenyltin fluoride is used. The cocatalytic action of the tin compound consists in continuous formation of difluorotriphenylstannate anion that as the tetraalkyloammonium salt enter the solution where it reacts with alkyl halides to produce alkyl fluorides. The cocatalytic system was used to synthesis of 1,1-difluoroalkanes in two steps from aldehydes. A new kind of PTC was elaborated in which Ph₃SnF acts as phase transfer catalyst via continuous formation of potassium salts of diflurotriphenylstannate anions soluble in dipolar aprotic solvents. A new, simple and general method of synthesis of tetraalkylammonium and potassium salts of difluorotriorgano-tin, silicon and germanium anions is reported.     

Microwave-assisted polycondensation of aliphatic diols of isosorbide with aliphatic disulphonylesters via phase-transfer catalysis

Numerous polycondensations of aliphatic diol of isosorbide and 1,8-dimesyloctane or other aliphatic dibromo and disulphonated alkylating agent was performed under phase-transfer catalytic conditions. In order to check the possible specific non-thermal microwave (MW) effects, reactions were comparatively performed inside a thermostated oil bath (Δ) under similar conditions. The reactions conditions were varied to optimize both, the fraction insoluble in methanol (FP MeOH) and the molecular weight of polyethers. In all cases, it was found that microwave-assisted polycondensations proceeded more efficiently compared with conventional heating (the reaction time was reduced from 24 h to 30 min: ratio 1/50). The polycondensation under microwave yields 63% of polyethers precipitating in methanol with relatively high average-weight molecular weights (M_w up to approximately 7000). The polyethers were characterized by NMR (¹H, ¹³C) and FT-IR spectroscopy and SEC measurement and MALDI-TOF mass spectrometry.     

Liquid-phase oxidation of alkylaromatic hydrocarbons and their cyclohexyl derivatives to hydroperoxides in the presence of phthalimide catalysts

Regularities of liquid-phase oxidation the alkyl aromatic hydrocarbons and their cyclohexyl derivatives to hydroperoxides at presence of phthalimide catalysts are studied. It is established that N-hydroxylphthalimide increases the speed of oxidation of these hydrocarbons and provides high selectivity of formation of their hydroperoxides.     

Comparative study of chemically immobilized and conventional homogeneous ionic liquids as phase-transfer catalysts for the N-alkylation of heterocyclic compounds

Various ionic liquids (ILs) were screened for their phase-transfer catalytic (PTC) activity using the N-alkylation of nitrogen heterocycles as the model reaction. Immobilized ILs behaved extremely well and proved to be far better catalysts than conventional homogeneous PTCs in terms of their stability, easy recovery, and reusability. The investigation also demonstrated that quaternary tetraalkylammonium salts offer very high catalytic activity, whereas aromatic heterocyclic tetravalent nitrogen catalysts (imidazolium- and pyridinium-based salts) were poorly active.     

Direct transformation of benzilic amines to carbonyls using polyacrylamide-bound tungstate under phase-transfer catalysis conditions

A recyclable catalytic system under heterogeneous phase-transfer catalysis conditions was designed by using polyacrylamide-bound tungstate. A convenient method for the oxidative direct transformation of benzilic amines to carbonyls with hydrogen peroxide was then developed.     

Highly enantioselective alkylation of glycine methyl and ethyl ester derivatives under phase-transfer conditions: its synthetic advantage

Phase-transfer alkylation of the benzophenone Schiff base of glycine methyl or ethyl ester (2) was found to be catalyzed by 3,4,5-F₃-C₆H₂-NAS-Br [(S,S)-1] with high efficiency and excellent enantioselectivity. This procedure allows facile derivatization of the resulting alkylation products to other synthetically useful chiral building blocks.     

Effect of Brønsted acid co-catalyst in asymmetric conjugate addition of 3-aryloxindoles to maleimide under base-free phase-transfer conditions

Highly diastereo- and enantioselective conjugate addition of 3-aryloxindoles to maleimide was accomplished under base-free phase-transfer conditions. The effect of Brønsted acid co-catalyst was examined, and we found that the use of a phenol derivative as co-catalyst was effective for obtaining the target conjugate adduct in good yield with high stereoselectivity.     

Microwave-assisted phase-transfer catalysis for the rapid one-pot methylation and gas chromatographic determination of phenolics

Microwave-assisted phase-transfer catalysis (PTC) is reported for the first time, for the one-step extraction–derivatization–preconcentration and gas chromatographic determination of twenty phenols and ten phenolic acids. The well established phase-transfer catalytic methylation is largely accelerated when heating is replaced with the “greener” microwave irradiation. The overall procedure was thoroughly optimized and the analytes were determined by GC/MS. The method presented adequate analytical characteristics being more sensitive in analyzing phenols than phenolic acids. The limits of detection without any additional preconcentration steps (e.g. solvent evaporation) were adequate and ranged from 0.4 to 15.8 ng/mL while limits of quantitation were between 1.2 and 33.3 ng/mL. The method was applied to the determination of phenols, in spiked environmental samples and phenolic acids in aqueous infusions of commercially available pharmaceutical dry plants. The recoveries of fortified composite lake water samples and Mentha spicata aqueous infusions ranged from 89.3% to 117.3% for phenols and 93.3% to 115.2% for phenolic acids.     

O-Alkylation of a lignite humic acid by phase-transfer catalysis

A mild phase-transfer catalytic reaction has been conducted to O-alkylate the acidic functions of a lignite humic acid (HA), using tetrabutylammonium hydroxide as the phase-transfer catalyst. The HA acidic functional groups were made to react, in tetrahydrofuran, by nucleophilic substitution with several alkyl halides—methyl iodide, and ethyl, propyl, and butyl, and benzyl bromide. The occurrence of the O-alkylation reaction was assessed by elemental analysis and ¹H NMR, CPMAS ¹³C NMR, and FTIR spectroscopy. Bonding of alkyl groups increased the carbon and hydrogen content and the H/C ratios of all the humic reaction products. Increased nitrogen in the reaction products suggested incomplete removal of the phase-transfer catalyst after purification of the alkylated HA. ¹H NMR and CPMAS ¹³C NMR spectra of alkylated products provided evidence of the successful occurrence of the alkylation reactions. Infrared spectra confirmed the NMR results, revealing the characteristic absorption of newly formed alkyl and aryl ethers and esters in the alkylated products and C–H stretching in the aromatic ring of the benzylated derivative. These findings indicate that humic matter can be successfully alkylated with several different alkylating groups by catalysed phase-transfer reaction. This O-alkylation reaction has the advantage of being mild, versatile, and high-yielding compared with traditional methylation reactions applied to HA. The possibility of introducing different alkyl groups into the HA by a mild phase-transfer reaction may become useful by enabling improved fractionation of humic supramolecular associations and further understanding of the molecular nature of humic substances.     

Liquid-phase catalytic processing of biomass-derived oxygenated hydrocarbons to fuels and chemicals

Biomass has the potential to serve as a sustainable source of energy and organic carbon for our industrialized society. The focus of this Review is to present an overview of chemical catalytic transformations of biomass-derived oxygenated feedstocks (primarily sugars and sugar-alcohols) in the liquid phase to value-added chemicals and fuels, with specific examples emphasizing the development of catalytic processes based on an understanding of the fundamental reaction chemistry. The key reactions involved in the processing of biomass are hydrolysis, dehydration, isomerization, aldol condensation, reforming, hydrogenation, and oxidation. Further, it is discussed how ideas based on fundamental chemical and catalytic concepts lead to strategies for the control of reaction pathways and process conditions to produce H(2)/CO(2) or H(2)/CO gas mixtures by aqueous-phase reforming, to produce furan compounds by selective dehydration of carbohydrates, and to produce liquid alkanes by the combination of aldol condensation and dehydration/hydrogenation processes.     

Flocculation of anionic surfactant micelles in the presence of hydrocarbons

Adsorptive micellar flocculation (AMF) is a surfactant-based separation process based on the flocculation of micelles of suitable anionic surfactants by Al³⁺. The micelles form large amorphous flocs which can be removed by filtration, which is attractive because soluble pollutants are captured by the floc, thus providing a simple separation method. As the primary aim of AMF is the removal of anionic pollutants from aqueous streams, it is important to investigate the influence of the various substances which may affect it. This article discusses the influence of the presence of insoluble hydrocarbons on the flocculation of micelles of the anionic surfactant dodecyl sulfate by Al³⁺. The ratio between surfactant remaining in solution and total surfactant and the ratio between Al³⁺ and surfactant in the flocculate are determined in systems composed of an aqueous solution containing a constant dodecyl sulfate concentration of 0.05 M and a variable Al³⁺ concentration and an organic phase (decane) with phase volume ratios of decane/water ranging from 0 (no decane) to 0.15. The flocculation is only slightly affected by the presence of decane for decane/solution ratios below 0.05, while the effect (lower flocculated fraction) is more marked above this ratio. Received: 25 October 1999/Accepted: 7 February 2000     

Liquid-phase oxidation of anthracene by hydrogen peroxide in the presence of heterogenized vanadyl acetylacetonate

The synthesis of heterogenized vanadyl acetylacetonate was accomplished by alkylation of a chloromethylated styrene—divinylbenzene copolymer via activation by Co(II) complexes. The effect of heterogenization on the structure of the complexes and their catalytic properties in the peroxide oxidation of anthracene was investigated by kinetic studies and EPR spectroscopy. Increased stability during oxidation of the catalytic centers of the polymer sample as compared with homogeneous vanadyl acetylacetonate was demonstrated.Department of Fine Organic Synthesis, Institute of Chemistry, Bashkir Science Center, Ural Branch, Russian Academy of Sciences, Ekaterinburg 620219. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 800–804, April, 1992.