Microwave-assisted ammonium formate-mediated Knoevenagel reaction under solvent-free conditions – a green method for C–C bond formation

Abstract

Syntheses of structurally varied densely functionalized olefins have been accomplished (23 examples) through microwave-assisted ammonium formate-mediated Knoevenagel condensation of differently substituted aromatic aldehydes with ethyl cyanoacetate, cyanoacetamide, malononitrile, and malonic acid under solvent-free condition in good yield (76–95%) and high purity. The said reactions occur within very short period of time (0.75–3 min) in eco-friendly conditions involving an operationally simple procedure, eliminating any kind of inorganic support, toxic reagent and organic solvent.     

Oxidations of some α-amino acids under mitsunobu reaction conditions

Reactions of α-amino acids with azodicarboxylates and Ph₃P results in oxidation at the α-carbon. N-acyl or carbamoyl amino acid esters give azodicarobxylate adducts, whereas free α-amino acid esters are converted to the corresponding α-keto esters.     

Microwave-assisted ammonium formate-mediated synthesis of Hanstzch dihydropyridines under solvent-free conditions – a green protocol

Abstract

Microwave-assisted ammonium formate-mediated eco-friendly synthesis of structurally varied Hantzsch dihydropyridines under solvent-free conditions has been successfully accomplished with good yield, minimization of toxic reagents and organic solvents in the process. The elimination of the inorganic support decreased the disposal problem and the extremely small reaction time minimized energy dissipation.     

Do reaction conditions affect the stereoselectivity in the Staudinger reaction?

The stereochemistry is one of the critical issues in the Staudinger reaction. We have proposed the origin of the stereoselectivity recently. The effects of solvents, additives, and pathways of ketene generation on the stereoselectivity were investigated by using a clean Staudinger reaction, which is a sensitive reaction system to the stereoselectivity. The results indicate that the additives, usually existed and generated in the Staudinger reaction, and the pathways of the ketene generation do not generally affect the stereoselectivity. The solvent affects the stereoselectivity. The polar solvent is favorable to the formation of trans-beta-lactams. The addition orders of the reagents affect the stereoselectivity in the Staudinger reaction between acyl chlorides and imines. The addition of a tertiary amine into a solution of the acyl chloride and the imine generally decreases the stereoselectivity, which is affected by the interval between additions of the acyl chloride and the tertiary amine, and the imine substituents. Our current results provide further understanding on the stereochemistry of the Staudinger reaction between acyl chlorides and imines and on the factors affecting the stereochemistry and also provide a method to prepare beta-lactams with the desired relative configuration via rationally tuning the stereoselectivity-controlling factors in the Staudinger reaction.     

β-Oxo-sulfoxide rearrangements under sila-Pummerer reaction conditions

Under sila-Pummerer reaction conditions, the β-oxo-sulfoxide 1 gave rise to a new pentacyclic compound 5. The structure of 5 was deduced from spectral data and by X-ray analysis of the sulfoxide 6 which was formed by subsequent oxidation.     

Transition-metal catalysis in michael addition of β-dicarbonyls : Tuning of the reaction conditions

(2,4- Pentanedionato) copper(I) and bis(2,4-pentanedionato)copper(II) together with boron trifluoride etherate catalyze Michael addition of β-dicarbonyls to cyclohexenone, cyclopentenone, 2-methylcyclopentenone, and 3-thienylidenemalonaldehyde.     

Aza-Michael reaction of 12-N-carboxamide of (–)-cytisine under high pressure conditions

The first example of aza-Michael reaction of 12-N-carboxamide of quinolizidine alkaloid (–)-cytisine with α,β-unsaturated ketones, dimethyl acetylenedicarboxylate and β-nitrostyrene under high pressure condition has been described. It has been shown that the [4+2]-cycloaddition takes place in the case with N-phenylmaleimide.     

Microwave-assisted Kornblum oxidation of organic halides

Microwave-assisted Kornblum oxidation is proved to be an effective way to obtain aldehyde and ketones from their corresponding chlorides. Under microwave irradiation, not only the reaction time was greatly decreased, due to avoiding the by-product, the yield was increased. It is noteworthy that the scope of the method was broadly expanded.     

Microwave-assisted synthesis of fused pyrazolo[3,4-b]pyrazines by the reaction of ortho-aminonitrosopyrazoles and cyclic β-diketones

Novel fused pyrazolo[3,4-b]pyrazines 3 were prepared by assisted microwave cyclocondensation reaction of ortho-aminonitrosopyrazoles 1 and cyclic β-diketones 2 in dimethylformamide. This protocol provides a simple procedure for the synthesis of the title compounds with the advantages of easy work-up, mild reaction conditions and good yields.     

Microwave-assisted synthesis of dialkyl ω-azidoalkylphosphonates

An efficient and reproducible microwave-assisted synthesis of dialkyl ω-azidoalkylphosphonates via nucleophilic substitution of the appropriate dialkyl ω-bromoalkylphosphonates by sodium azide in water or dimethylformamide (DMF) as solvent has been developed. This process has been optimized for batch reactors. The target, structurally diverse dialkyl ω-azidoalkylphosphonates with different steric hindrance around the phosphonato groups and containing unbranched side carbon chains of different lengths (n?=?2–6), has been obtained in moderate to high yields (39–87%).     

Effect of reaction conditions on surface properties of TEOS–TBOT–PDMS hybrid materials

Hybrid materials based on tetraethoxysilane (TEOS), tetrabutyl orthotitanate (TBOT), and hydroxyl terminated polydimethyl siloxane (PDMS) have been prepared and characterized. The effects of HCl concentration and PDMS molecular weight (M_W) have been analysed. The physical and chemical characteristics have been discussed based on the results obtained from the characterization by Raman spectroscopy, nitrogen adsorption, mercury intrusion porosimetry and inverse gas chromatography (IGC). Specific surface areas (SSA) and pore volumes increase with HCl concentration and are independent on the PDMS Mw. SSA values as high as 300 m² g⁻¹ have been obtained for hybrid materials prepared with HCl:(TEOS + TBOT) concentration of 0.3 and PDMS Mw of 550 g mol⁻¹. These materials present the higher pore volumes and lower pore sizes. However, for HCl:(TEOS + TBOT) concentration of 0.5, only macroporous materials are obtained with SSA values as low as 2–4 m² g⁻¹, and pore sizes close to 10 μm. In general the presence of Ti on the SSA and porosities give a little decrease in such values. Surface energies are consistent with those of organic–inorganic materials. Dispersive surface energies are higher for the Si–Ti hybrid materials and, for all of them, they decrease with both HCl concentration and PDMS Mw. This result can be assigned to the presence of a higher concentration of PDMS (or CH₃ groups) on the surface of the hybrid material as well as the presence of disordered anatase-like structures. On the other hand, the acid and base properties are dependent on both HCl concentration and PDMS Mw. It has been observed that the acid and base parameters of the Si–Ti hybrid materials are influenced by the disorder degree of the amorphous titanium oxide present in them. As the disorder decrease both acid and base parameters increase.     

Unusual formation of β-carboline dimers under Bischler-Napieralski reaction conditions: an old reaction with a new direction

l-N-Formyl tryptophan methyl ester (3) underwent a Bischler-Napieralski reaction with POCl₃ at room temperature or under microwave irradiation, resulting in the unusual formation of β-carboline dimers 5 and 6. Most importantly, acetylation using Ac₂O of each of the dimers 5 and 6 separately afforded 1-[3′-carbomethoxy-β-carbolinyl]-3-carbomethoxy-9-acetyl-β-carboline (7) as the only product, the structure of which was confirmed by X-ray crystallography studies.     

Microwave-assisted organocatalytic enantioselective intramolecular aza-Michael reaction with α,β-unsaturated ketones

An organocatalytic enantioselective intramolecular aza-Michael reaction of carbamates bearing conjugated ketones as Michael acceptors is described. By using 9-amino-9-deoxy-epi-hydroquinine as the catalyst and pentafluoropropionic acid as a co-catalyst, a series of piperidines, pyrrolidines, and the corresponding benzo-fused derivatives (indolines, isoindolines, tetrahydroquinolines, and tetrahydroisoquinolines) can be obtained in excellent yields and enantioselectivities. In addition, the use of microwave irradiation at 60 °C improves the efficiency of the process giving rise to the final products with comparable yields and enantiomeric excesses. Some mechanistic insights are also considered.     

Microwave-assisted synthesis of 6-amino-β-cyclodextrins

A general microwave-assisted procedure for the synthesis of 6-amino-β-cyclodextrins is reported. Mono-tosyl-β-cyclodextrin was used as the starting material in a one-pot route employing a solvent-free microwave-assisted reaction with a liquid amine. Shorter reaction times were observed for the formation of 6-amino-β-cyclodextrins using this novel microwave approach compared to the thermal procedure.     

Microwave-assisted reaction of peptide formation by amino acid with phosphate:Exploration of the most possible channels for the origin of life

The formation of peptides and then protein by small abiological molecules clusters such as amino acid is a key stage in the origin of life[1]. More and more ex- perimental results showed that phosphate plays an important role in the formation of biomolecules in prebiotic chemical evolution. The principal reservoirs of biochemical energy are phosphates (such as ATP). The peculiar role of phosphates in contemporary life might suggest its essential role in prebiotic energy conversion, syntheses …     

Microwave-assisted synthesis of α-aminophosphine oxides by the Kabachnik–Fields reaction applying amides as the starting materials

A series of acylated α-aminophosphine oxides were synthesized by the microwave-assisted Kabachnik–Fields reaction of a series of carboxylic acid amides, formaldehyde and secondary phosphine oxides. To compensate the lower reactivity of the –NH₂ reagents, they had to be used in an excess. The solvolytic condensations furnished the α-aminophosphine oxides in yields of 58–93% after purification by chromatography.     

Unexpected formation of β, meso-directly linked diporphyrins under Adler–Longo reaction conditions

Unexpected formation of β, meso-directly linked diporphyrin products has been described in the reactions of β-formyl porphyrins with pyrrole under Adler–Longo reaction conditions. Preliminary mechanistic studies indicates that β-dipyrromethane substituted porphyrin structure is the crucial intermediate for the formation of diporphyrin product.     

The reaction of β-lactam carbenes with 3,6-di(2-pyrimidinyl)tetrazine: regulating products by reaction conditions

The reaction of β-lactam carbenes with 3,6-di(2-pyrimidinyl)tetrazine was studied, which produced good yields of novel 5-(3-[1,2,3]triazolo[1,5-a]pyrimidinyl)pyrrol-2-ones or pyrrolo[3′,2′:3,4]pyrrolo[1,2-a]pyrimidin-2-ones under heating at 100 °C or 140 °C, respectively. This work provided a highly efficient strategy for the construction of both [1,2,3]triazolo[1,5-a]pyrimidine and pyrrolo[3′,2′:3,4]pyrrolo[1,2-a]pyrimidine ring systems from the same reactants, and extended the application of β-lactam carbenes in the syntheses of complex heterocycles.     

Synthesis of β-triazolyl sulfones via the reaction of vinyl sulfones with 1,2,4-triazoles under basic conditions

Russian Chemical Bulletin - A method was developed for the synthesis of β-triazolyl sulfones from vinylsulfones and 1,2,4-triazoles in the presence of sodium triazolide taken as the base. The...