Aliphatic Cyclic Ketones Research Articles

Light-enhancing ketone transfer hydrogenation catalyzed by diphosphine phenanthroline ruthenium complexes

The cationic phenanthroline ruthenium derivatives [Ru(OAc)(dppb)(NN)]OAc (NN = phen 1, imidazo[4,5-f][1,10]phenanthroline 2) have been obtained in high yield by reaction of the acetate [Ru(OAc)2dppb] with the corresponding NN ligand. The dinuclear cyclometalated [(dppb)(η2-OAc)(Ru(µ-NN-phenimid-NC)Ru(η2-OAc)(dppb)]OAc (3) has been prepared from 2 with [Ru(OAc)2(dppb)] via elimination of acetic acid. The characterization of these compounds has been carried out by NMR, FT-IR, UV–Vis, conductivity and cyclic voltammetry measurements. These derivatives display catalytic activity in the transfer hydrogenation of aromatic and aliphatic cyclic ketones at S/C up to 2000 in presence of NaOiPr in 2-propanol. An increase of the rate (up to 8 times) has been observed upon irradiation at 30 and 60 °C (300 W Xenon Arc Lamp light source). Control experiments show that [Ru(OiPr)2(dppb)(phen)] (1A), formed from 1 by substitution of the acetate with the isopropoxide ligand, shows a stronger emission compared to 1 and that 1A is quenched by NaOiPr, affording the dihydride [Ru(H)2(dppb)(phen)] (1C) via a photo induced β-H elimination.

Ketones in Low-Temperature Oxidation Products of Crude Oil

Ketone compounds are oxidation products of crude oil in the in-situ combustion (ISC) process. Revealing the molecular composition of ketones can provide theoretical guidance for understanding the oxidation process of crude oil and valuable clues for studying the combustion state of crude oil in the reservoir. In this study, low-temperature oxidation (LTO) processes were simulated in thermal oxidation experiments to obtain thermally oxidized oil at different temperatures (170 °C, 220 °C, 270 °C, and 320 °C). A combination of chemical derivatization and positive-ion electrospray (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was used to analyze the molecular composition of different kinds of ketones (fatty ketones, naphthenic ketones, and aromatic ketones) in the oxidized oils at different temperatures. The results showed that the concentration of aliphatic ketones and aliphatic cyclic ketones in the product oils decreased with the increase in temperature, while aromatic ketones increased with the increase in temperature. At the same oxidation temperature, the content of ketones follows this order: fatty ketones < cycloalkanes < aromatic ketones. The concentrations of ketones reached their maximum value at 170 °C and decreased at high temperatures due to over-oxidation. It was also found that nitrogen-containing compounds are more easily oxidized to ketone compounds than their hydrocarbon counterparts in the LTO process.

The Synthesis of Sn-Containing Silicates Coated with Binaphthol and Their Specific Application for Catalytic Synthesis of 6-Hydroxyhexanoic Acid and Cyclohexylformate through Baeyer-Villiger Oxidation

The Baeyer–Villiger oxidation (BVO) of ketone and aldehyde can produce ester and formate, which both have wide applications in many areas. In this work, a series of Sn-containing silicates were prepared through the sol-gel process by using structure-directing and crystallizing agents and post-synthetic coordinated modification of binaphthol. Characterizations revealed that loading of (L)-sodium lactate as the crystallizing agent decreased the crystal size of the synthesized catalyst, and there were SnO2 nanoparticles with sizes of 17–19 nm on the catalyst. Furthermore, quite differently from the 3D mesoporous structure of classical Sn-beta zeolites, the synthesized catalysts had a silt-like mesoporous structure. In the catalysis, when cyclic aliphatic ketones were used as the substrate, only BVO-type products and corresponding ring-opening products were obtained. BVO of aliphatic aldehyde produced both an aerobic oxidation product (carboxylic acid) and a BVO-type product. The presented transformation of aromatic aldehyde (benzaldehyde) only gave an aerobic oxidation product (benzoic acid). The post-synthetic coordinating attachment of (S)-binaphthol to the Sn-containing silicate backbone worsened the BVO of aliphatic ketones but improved the BVO of aliphatic aldehyde and the aerobic oxidation of aromatic aldehyde. In addition, this work also developed two new routes for the synthesis of high-value-added 6-hydroxyhexanoic acid and cyclohexylformate under catalytic BVO conditions.

The Al-Containing Silicates Modified with Organic Ligands and SnO2 Nanoparticles for Catalytic Baeyer-Villiger Oxidation and Aerobic Carboxylation of Carbonyl Compounds.

The Baeyer-Villiger Oxidation (BVO) of ketones and aldehydes produce lactones and formates, while aerobic carboxylation of aldehydes manufactures carboxylic acids, both having high added value. This work prepared a series of Al-containing silicates modified with organic ligands and SnO2 nanoparticles, which were then employed as catalyst in BVO and carboxylation. Characterizations revealed the morphology of the synthesized catalyst was changed from micron-sized thin sheets to smaller blocks, and then to uniform nanoparticles (size of 50 nm) having the doped SnO2 nanoparticles with a size of 29 nm. All catalysts showed high BET surface areas featuring silt-like mesopores. In determining the priority of BVO and carboxylation, an influence evaluation of the parameters showed the order to be substrate > oxidant > solvent > catalyst. Cyclic aliphatic ketones were suitable for BVO, but linear aliphatic and aromatic aldehydes for carboxylation. Coordination of (S)-binaphthol or doping of Sn into catalyst showed little influence on BVO under m-CPBA, but the Sn-doped catalyst largely increased BVO under (NH4)2S2O8 and H2O2. Calculations revealed that the catalyst containing both Al and Sn could give BVO intermediates lower energies than the Sn-beta zeolite model. The present system exhibited merits including wider substrate scope, innocuous catalytic metal, greener oxidant, as well as lower catalyst cost.

Syntheses of N-acylhydrazones of 2-hydroxy-3,5-dinitrobenzohydrazide, and their Conversion into 3-Acetyl-2,3-dihydro-1,3,4-oxadiazole

N-Acylhydrazones 11-17 were prepared via reaction of 2-hydroxy-3,5-dinitrobenzohydrazide 3 with aromatic aldehydes 4-6 or with aromatic ketone 7 or aliphatic acyclic ketone 8 and cyclic aliphatic ketones 9-10 under reflux in ethanol. Conversion of hydrazide hydrazone 17 into N-acetyl-1,3,4-oxadiazole derivative 19 was achieved via reaction with acetic anhydride 18. The products were characterized by MS, 1H-NMR and 13C-NMR. The structure of 19 was confirmed by X-ray analysis. Compound 19 was evaluated for in vitro antibacterial activity against two microorganisms (S. aureus and E. coli ). The obtained results showed that this compound has good inhibition against the tested bacterial pathogens by micro-dilution method with MIC 15.1 μg.

3D-Network porous polymer bonded metalloporphyrin: An efficient and reusable catalyst for the Baeyer-Villiger oxidation

A new, green catalyst was prepared through immobilization of metalloporphyrin on the surface of 3D-network polymer based on calix[4]resorcinarene (PC4RA), which efficiently catalyze B-V oxidation reaction using O2/benzaldehyde. The catalyst demonstrated excellent activity, which is highly potential for cyclic aliphatic ketones oxidation under mild conditions. IR spectroscopy, UV-Vis spectroscopy, thermal gravimetric analysis, energy dispersive spectroscopy and scanning electron microscopy are some of the spectroscopic methods used to characterize the new synthesized solid support.

Application of Ketoreductase in Asymmetric Synthesis of Pharmaceuticals and Bioactive Molecules: An Update (2018-2020).

With the rapid development of genomic DNA sequencing, recombinant DNA expression, and protein engineering, biocatalysis has been increasingly and widely adopted in the synthesis of pharmaceuticals, bioactive molecules, fine chemicals, and agrochemicals. In this review, we have summarized the most recent advances achieved (2018-2020) in the research area of ketoreductase (KRED)-catalyzed asymmetric synthesis of chiral secondary alcohol intermediates to pharmaceuticals and bioactive molecules. In the first part, synthesis of chiral alcohols with one stereocenter through the bioreduction of four different ketone classes, namely acyclic aliphatic ketones, benzyl or phenylethyl ketones, cyclic aliphatic ketones, and aryl ketones, is discussed. In the second part, KRED-catalyzed dynamic reductive kinetic resolution and reductive desymmetrization are presented for the synthesis of chiral alcohols with two contiguous stereocenters.

Engineered Artificial Carboligases Facilitate Regioselective Preparation of Enantioenriched Aldol Adducts.

Controlling regio- and stereoselectivity of aldol additions is generally challenging. Here we show that an artificial aldolase with high specificity for acetone as the aldol donor can be reengineered via single active site mutations to accept linear and cyclic aliphatic ketones with notable efficiency, regioselectivity, and stereocontrol. Biochemical and crystallographic data show how the mutated residues modulate the binding and activation of specific aldol donors, as well as their subsequent reaction with diverse aldehyde acceptors. Broadening the substrate scope of this evolutionarily naïve catalyst proved much easier than previous attempts to redesign natural aldolases, suggesting that such proteins may be excellent starting points for the development of customized biocatalysts for diverse practical applications.

Regioselective Synthesis of Fused Furans by Decarboxylative Annulation of α,β‐Alkenyl Carboxylic Acid with Cyclic Ketone: Synthesis of Di‐Heteroaryl Derivatives

Abstractα,β‐Alkenyl carboxylic acids undergo CuII‐mediated decarboxylative annulation reactions with aliphatic cyclic ketones to provide synthetically valuable di‐heterocycles. The annulation process tolerates a variety of aliphatic ketones and heterocyclic alkenyl carboxylic acids, producing substituted fused furan derivatives with complete regioselectivity. The current protocol offers a synthetically applicable pathway to construct a variety of oligo‐heterocycles through Cu‐mediated single‐electron transfer and decarboxylation. Notably, synthesis of relatively inaccessible di‐heterocycles has been achieved successfully using this protocol.

Regioselective Synthesis of Fused Furans by Decarboxylative Annulation of α,β-Alkenyl Carboxylic Acid with Cyclic Ketone: Synthesis of Di-Heteroaryl Derivatives.

α,β-Alkenyl carboxylic acids undergo CuII -mediated decarboxylative annulation reactions with aliphatic cyclic ketones to provide synthetically valuable di-heterocycles. The annulation process tolerates a variety of aliphatic ketones and heterocyclic alkenyl carboxylic acids, producing substituted fused furan derivatives with complete regioselectivity. The current protocol offers a synthetically applicable pathway to construct a variety of oligo-heterocycles through Cu-mediated single-electron transfer and decarboxylation. Notably, synthesis of relatively inaccessible di-heterocycles has been achieved successfully using this protocol.

Biocatalytic Aldol Addition of Simple Aliphatic Nucleophiles to Hydroxyaldehydes.

Asymmetric aldol addition of simple aldehydes and ketones to electrophiles is a cornerstone reaction for the synthesis of unusual sugars and chiral building blocks. We investigated d-fructose-6-phosphate aldolase from E. coli (FSA) D6X variants as catalysts for the aldol additions of ethanal and nonfunctionalized linear and cyclic aliphatic ketones as nucleophiles to nonphosphorylated hydroxyaldehydes. Thus, addition of propanone, cyclobutanone, cyclopentanone, or ethanal to 3-hydroxypropanal or (S)- or (R)-3-hydroxybutanal catalyzed by FSA D6H and D6Q variants furnished rare deoxysugars in 8–77% isolated yields with high stereoselectivity (97:3 dr and >95% ee).

ChemInform Abstract: Copper‐Catalyzed Aerobic Synthesis of 2‐Arylpyridines from Acetophenones and 1,3‐Diaminopropane.

AbstractNot only a range of electronically diverse acetophenones undergo this transformation but also aryl ketones with a longer alkyl chain, as well as cyclic aliphatic ketones.

Synthesis, spectral, and structural characteristics of cyanohydrines derived from aliphatic cyclic ketones

A series of cyanohydrines derived from cyclic aliphatic ketones was synthesized by acid-catalyzed nucleophilic addition reaction under the action of potassium cyanide. The products were characterized by means of multi-nuclear NMR spectroscopy (1H, 13C, 14N, 15N), mass spectrometry, elemental analysis, UV-Vis spectroscopy, refraction index measurements as well as vibrational spectroscopy. The structure of the cyanohydrine of cyclohexanone was elucidated by means of single crystal X-ray diffraction.

Mapping the internal recognition surface of an octanuclear coordination cage using guest libraries.

Size and shape criteria for guest binding inside the cavity of an octanuclear cubic coordination cage in water have been established using a new fluorescence displacement assay to quantify guest binding. For aliphatic cyclic ketones of increasing size (from C5 to C11), there is a linear relationship between ΔG for guest binding and the guest's surface area: the change in ΔG for binding is 0.3 kJ mol(-1) Å(-2), corresponding to 5 kJ mol(-1) for each additional CH2 group in the guest, in good agreement with expectations based on hydrophobic desolvation. The highest association constant is K = 1.2 × 10(6) M(-1) for cycloundecanone, whose volume is approximately 50% of the cavity volume; for larger C12 and C13 cyclic ketones, the association constant progressively decreases as the guests become too large. For a series of C10 aliphatic ketones differing in shape but not size, ΔG for guest binding showed no correlation with surface area. These guests are close to the volume limit of the cavity (cf. Rebek's 55% rule), so the association constant is sensitive to shape complementarity, with small changes in guest structure resulting in large changes in binding affinity. The most flexible members of this series (linear aliphatic ketones) did not bind, whereas the more preorganized cyclic ketones all have association constants of 10(4)-10(5) M(-1). A crystal structure of the cage·cycloundecanone complex shows that the guest carbonyl oxygen is directed into a binding pocket defined by a convergent set of CH groups, which act as weak hydrogen-bond donors, and also shows close contacts between the exterior surface of the disc-shaped guest and the interior surface of the pseudospherical cage cavity despite the slight mismatch in shape.

Soybean (Glycine max) as a versatile biocatalyst for organic synthesis

A series of aliphatic and aromatic aldehydes and ketones were reduced using plant cell preparations of Glycine max seeds (soybean). The biotransformation of five aromatic aldehydes in water, at room temperature afforded the corresponding alcohols in excellent yields varying from 89 to 100%. Two prochiral aromatic ketones yielded the alcohol in very low conversion, 1% and to 4%; however with good enantiomeric excess (ee) of 99 and 79%, respectively. Additionally, three prochiral and one cyclic aliphatic ketones produced the corresponding alcohols in moderate yields varying from 10 to 58% and ee varying from 73 to 99%. Hydrolysis of two aromatic esters yielded the expected carboxylic acids in 49 and 66%. Most of the obtained alcohols have commercial value as cosmetic fragrances. Although, the enzymes present in soybean (reductase/lipase) has not been defined, the reaction is an important route for the preparation of pure alcohols and carboxylic acid, with low cost and environmental impact. Keywords: Glycine max , biocatalysis, bioreduction, aldehydes and ketones, ester hydrolysis

Use of cyclic aliphatic ketones for spiro 2-amino-3-cyano pyrano[3,2-c]chromene formation

The three component reaction between 4-hydroxycoumarin, malononitrile and carbonyl compounds in ethanol in the presence of morpholine as a catalyst was studied. Only cyclic aliphatic ketones afford spiro 2-amino-3-cyanopyrano(3,2-c)chromene derivatives.

Scandium-Catalyzed Homologation of Cycloalkanones with Diazo Compounds

The catalytic use of scandium(III) salts as Lewis acids allows the ring expansion of cyclic aliphatic ketones by carbon insertion from the reaction with diazo compounds obtained from ketones or aldehydes. The resulting monoalkylated or spiro ketones are obtained in very good yields.

Cloning, expression, characterization, and biocatalytic investigation of the 4-hydroxyacetophenone monooxygenase from Pseudomonas putida JD1.

While the number of available recombinant Baeyer-Villiger monooxygenases (BVMOs) has grown significantly over the last few years, there is still the demand for other BVMOs to expand the biocatalytic diversity. Most BVMOs that have been described are dedicated to convert efficiently cyclohexanone and related cyclic aliphatic ketones. To cover a broader range of substrate types and enantio- and/or regioselectivities, new BVMOs have to be discovered. The gene encoding a BVMO identified in Pseudomonas putida JD1 converting aromatic ketones (HAPMO; 4-hydroxyacetophenone monooxygenase) was amplified from genomic DNA using SiteFinding-PCR, cloned, and functionally expressed in Escherichia coli. Furthermore, four other open reading frames could be identified clustered around this HAPMO. It has been suggested that these proteins, including the HAPMO, might be involved in the degradation of 4-hydroxyacetophenone. Substrate specificity studies revealed that a large variety of other arylaliphatic ketones are also converted via Baeyer-Villiger oxidation into the corresponding esters, with preferences for para-substitutions at the aromatic ring. In addition, oxidation of aldehydes and some heteroaromatic compounds was observed. Cycloketones and open-chain ketones were not or poorly accepted, respectively. It was also found that this enzyme oxidizes aromatic ketones such as 3-phenyl-2-butanone with excellent enantioselectivity (E >>100).

Chemical Nuclear Polarization of Biradicals Created by Photolysis of Cyclic Aliphatic Ketones in the Gas Phase

Chemical nuclear polarization (CNP) of short-lived biradicals created in the photolysis of cyclic ketones in the gas phase with a buffer gas of CDCl3 molecules was studied theoretically and experimentally. The magnetoresonance and kinetic parameters were proposed for the biradicals. The experimental fact that the CNP of cycloundecanone in the gas phase and liquid was the strongest was confirmed by calculations. The computational results agree well with the experiment for both gas and liquid phases.

Chemoselective thioacetalisation and transthioacetalisation of carbonyl compounds catalysed by tetrabutylammonium tribromide (TBATB)Dedicated to Professor Subramanian Ranganathan on the occasion of his 70th birthday.

Thioacetals and thioketals of various aldehydes and ketones were obtained directly from carbonyl compounds or by a transthioacetalisation process from cyclic O,O-acetals in the presence of dithiols and a catalytic amount of tetrabutylammonium tribromide (TBATB). Chemoselective thioacetalisation of aromatic aldehydes containing an electron-donating group in the presence of an aldehyde containing an electron-withdrawing group, aldehydes in the presence of ketones, aliphatic cyclic ketones in the presence of aromatic ketones and less hindered ketones in the presence of more hindered ketones have been achieved. A cyclic acetal containing an electron-donating group has been chemoselectively transthioacetalised in the presence of an acetal having an electron-withdrawing substituent. These selectivities are due to the intrinsic reactivity of the substrate themselves and are independent of the catalyst and reaction conditions. Shorter reaction times, mild reaction conditions, stability of acid sensitive protecting groups, high efficiencies, facile isolation of the desired products and the catalytic nature of the reagent are the attractive features of the present method.