Deoxybenzoin Derivatives Research Articles

Synthesis of deoxybenzoins from β-alkoxy styrenes and arylboronic acids via palladium-catalyzed regioselective Heck-arylation reactions.

Palladium-catalyzed synthesis of deoxybenzoin derivatives from styryl ethers and arylboronic acids is reported. The reaction proceeds under mild conditions in the presence of TEMPO and provides the desired products in good to excellent yields. Simple operation, broad substrate scope, and functional group tolerance are the salient features of the developed methodology.

Synthesis of 9,10‐Dibenzoyl‐phenanthrene Derivatives Through a Palladium‐Catalyzed Domino Approach

AbstractA palladium‐catalyzed domino approach toward synthetically challenging phenanthrene derivatives has been developed. The procedure involves a sequence of oxidative homocoupling, cyclization, and oxidation starting from deoxybenzoin derivatives halogenated in the ortho position. Good assembly efficiency and good functional group tolerance have been observed with yields from moderate to excellent. A plausible reaction mechanism has been proposed based on experimental results and literature data.

Aqueous α‐Arylation of Mono‐ and Diarylethanone Enolates at Low Catalyst Loading

AbstractAcetophenone and deoxybenzoin derivatives are selectively α‐arylated using a combination of very small amounts of palladium acetate and diphenylphosphine oxide as catalyst system and water as the only solvent. Target di‐ and triarylethanones are isolated virtually free of metal residues, and the reaction is amenable to gram‐scale. A mechanistic proposal based on TEM images, poisoning experiments, kinetic plot and ESI‐MS spectrometry is also provided.magnified image

Synthesis of a deoxybenzoin derivative and its use as a flame retardant in poly(trimethylene terephthalate)

ABSTRACTA Friedel–Crafts acylation reaction was used to synthesize a deoxybenzoin derivative named bis[2,6‐dimethyl‐4‐(2‐phenyl acetyl)phenyl]phenyl phosphonate (BDPP), which could be used as a flame‐retardant additive in poly(trimethylene terephthalate) (PTT) resin. The limited oxygen index and cone calorimetry tests indicated that the introduction of 5 wt % BDPP significantly improved the flame‐retardant properties of PTT through a synergistic char‐formation mechanism in the condensed phase and a flame‐inhibition mechanism in the gas phase. The PTT–BDPP blend also demonstrated an evident reduction in the melt viscosity but a superior melt stability in comparison to the neat PTT. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45904.

ChemInform Abstract: Direct Copper‐Catalyzed α‐Arylation of Benzyl Phenyl Ketones with Aryl Iodides: Route Towards Tamoxifen.

AbstractThis is the first efficient α‐arylation of non‐activated deoxybenzoin derivatives with simple aryl iodides.

Estrogenic effect of three substituted deoxybenzoins

Deoxybenzoins (1-(2,4-dihydroxyphenyl)-2-(4-hydroxyphenyl)ethanone) are possible precursors or metabolites of isoflavanones which may have xenoestrogenic potential on estrogen receptor (ER). In this study we evaluated three 2′-substituted deoxybenzoin derivatives for their estrogenic effect based upon their ability to affect the proliferation of ERα+ MCF7 cells, ERβ+ PC3 cells and Hep2 cells stably transfected and expressing either ERα or ERβ. These compounds designated as CMPD3, CMPD6 and CMPD9 had –COOH, –(CH2)4–CH3 and –CH3 substitutions, respectively on the 2′-position of the 2,4-dihydroxyphenyl ring of deoxybenzoin. We found that all three compounds increased the proliferation of ERα+ MCF7 cells (EC50∼1–12μM) and ERα+ Hep2 cells, while causing apoptosis in ERβ+ PC3 cells (IC50∼1–5μM) and ERβ+ Hep2 cells. The compounds also up-regulated the expression of estrogen sensitive genes, trefoil factor 1 (TFF1, previously known as pS2) and cathepsin-D (CTSD), in these cells. We performed in vitro ER transcription activation assays using Hep2 cells transiently co-transfected with estrogen response element driven luciferase and either ERα or ERβ vectors to ascertain the mechanism of action of these compounds through the ‘classical’ genomic pathway of estrogenic activity and to determine their ER subtype selectivity. Molecular docking of the compounds with the Ligand Binding Domain of ERα and ERβ showed similar docking scores (Glidescores of −6.5 to −8.5kcal/mol) indicating that these compounds were ligands of both ERα and ERβ with similar affinity.

Direct Copper‐Catalyzed α‐Arylation of Benzyl Phenyl Ketones with Aryl Iodides: Route towards Tamoxifen

This is the first efficient α-arylation of non-activated deoxybenzoin derivatives with simple aryl iodides.

ChemInform Abstract: A Facile Synthesis of Benzo(b)thiophene Derivatives.

Lithiation of S-(2-methylphenyl) N, N, N', N'- tetramethylphosphorodiamidothioate with sec-BuLi at #75105° gave the corresponding benzylic anion which was acylated with various aromatic esters to give various deoxybenzoin derivatives in moderate to high yields. Acidic treatment of these products in refluxing formic acid gave 2-arylbenzo[b]thiophene derivatives. 2-Methylbenzo[b]thiophene and benzo[b]thiophen-2(3H)-one were also prepared using the similar procedure

Design, Synthesis, and Immunosuppressive Activity of New Deoxybenzoin Derivatives

In the search for potential immunosuppressive agents with high efficacy and low toxicity, a series of new deoxybenzoins were synthesized and evaluated for their cytotoxicity and immunosuppressive activity. Among the synthesized compounds, four deoxybenzoin oximes (compounds 31, 32, 37, and 38) exhibited lower cytotoxicity and higher inhibitory activity toward anti-CD3/anti-CD28 co-stimulated T-cell proliferation than other compounds. More significantly, compound 31 is >100-fold less cytotoxic than cyclosporine A (CsA) and is also more potent (31: SI>684.64, CsA: SI=235.44). The preliminary inhibition mechanism of compound 31 was also identified by flow cytometry, and this compound exerts immunosuppressive activity by inducing apoptosis in activated lymph node cells in a dose-dependent manner. In addition, the mechanism of apoptosis was detected by western blot analysis.

Metronidazole–Deoxybenzoin Derivatives as Anti‐Helicobacter pylori Agents with Potent Inhibitory Activity against HPE‐Induced Interleukin‐8

A series of new metronidazole-deoxybenzoin derivatives were synthesized and evaluated for their antimicrobial activity against Helicobacter pylori. Highly selective anti-H. pylori activity was also observed in synthesized compounds. Compound 34 exhibited the most potent activity, similar to the positive control amoxicillin. Furthermore, compounds 17 and 34 were able to significantly decrease H. pylori water extract (HPE)-induced production of interleukin-8 (IL-8) in gastric mucosal cells, which did not show any effect on the cell viability.

Design and synthesis of novel deoxybenzoin derivatives as FabH inhibitors and anti-inflammatory agents

β-Ketoacyl-acyl carrier protein synthase III (FabH) catalyzes the initial step of fatty acid biosynthesis via a type II fatty acid synthase in most bacteria. The important role of this essential enzyme combined with its unique structural features and ubiquitous occurrence in bacteria has made it an attractive new target for the development of new FabH inhibitors. The synthesis and biological evaluation halide-deoxybenzoins derivatives are described in this Letter. Potent FabH inhibitory and selective anti-Gram-negative bacteria activities were observed in deoxybenzoin derivatives. Furthermore, compound 19 was able to reduce the ECE-induced IL-8 production in gastric mucosal cells significantly. Based on the biological data and molecular docking, compound 19 is a potential FabH inhibitor and anti-inflammatory agent deserving further research.

1-(3,4-Dihydroxyphenyl)-2-(4-hydroxyphenyl)ethanone

The title compound, C14H12O4, is a deoxy­benzoin derivative in which the dihedral between the carbonyl group and the catechol unit is 5.99 (3)°. The dihedral angle between the two benzene rings is 60.26 (13)°. In the crystal structure, inter­molecular O—H⋯O hydrogen bonds connect mol­ecules, forming a two-dimensional network. In addition, weak inter­molecular C—H⋯O hydrogen bonds and C—H⋯π contacts further stabilize the crystal structure.

ChemInform Abstract: Synthesis, Crystal Structure and Antimicrobial Activity of Deoxybenzoin Derivatives from Genistein.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Synthesis, crystal structure and antimicrobial activity of deoxybenzoin derivatives from genistein

A series of deoxybenzoin derivatives from genistein were synthesized and their structures were elucidated by 1H NMR, mass spectral data and micro analyses. The structures of 2, 7 and 10 were determined by single-crystal X-ray analysis. These obtained compounds were evaluated for their assayed antibacterial ( Bacillus subtilis, Escherichia coli, Pseudomonas fluorescence and Staphylococcus aureus) and antifungal ( Aspergillus niger, Candida albicans and Trichophyton rubrum) activities by MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide) method. Most compounds have displayed comparable antibacterial activity against bacterial. On the basis of the biological results, structure–activity relationships are discussed.

Synthetic model of a new deoxybenzoin derivative from Deguelia hatschbachii A.M.G. Azevedo

In this paper we describe the synthesis of 2 ́,4 ́-dimethoxy-8-(propyl-2-one)-deoxybenzoin, anew compound employed as a model for the comparison with the respective spectral data for 6’,4-dihydroxy-3’-(3,3- dimethylallyl)-2",2"-dimethylchromene(5",6":5’,4’)-2’-methoxy-8-(propyl-2-one)deoxybenzoin, recently isolated from Deguelia hatschbachii A.M.G. Azevedo. Both compounds have a“propyl-2-one” group attached to C-8 of the deoxybenzoin skeleton, for which there is no precedent inthe literature. The Friedel-Crafts reaction of 1,3-dimethoxybenzene with phenylacetyl chloride furnished2 ́,4 ́-dimethoxydeoxybenzoin, that after reaction with allyl bromide gave 2 ́,4 ́-dimethoxy-8-(allyl)-deoxybenzoin. Wacker oxidation gave the desired model compound in 15% overall yield. The correspondingspectral data reinforced the structure previously determined for the natural product.

Synthetic model of a new deoxybenzoin derivative from Deguelia hatschbachii A.M.G. Azevedo

In this paper we describe the synthesis of 2´,4´-dimethoxy-8-(propyl-2-one)-deoxybenzoin, a new compound employed as a model for the comparison with the respective spectral data for 6',4-dihydroxy-3'-(3,3- dimethylallyl)-2",2"-dimethylchromene(5",6":5',4')-2'-methoxy-8-(propyl-2-one) deoxybenzoin, recently isolated from Deguelia hatschbachii A.M.G. Azevedo. Both compounds have a "propyl-2-one" group attached to C-8 of the deoxybenzoin skeleton, for which there is no precedent in the literature. The Friedel-Crafts reaction of 1,3-dimethoxybenzene with phenylacetyl chloride furnished 2´,4´-dimethoxydeoxybenzoin, that after reaction with allyl bromide gave 2´,4´-dimethoxy-8-(allyl)-deoxybenzoin . Wacker oxidation gave the desired model compound in 15% overall yield. The corresponding spectral data reinforced the structure previously determined for the natural product.

Kwakhurin, a Unique Isoflavone with Rejuvenating Activity from “Kwao Keur”: Further Characterization by 2D-NMR Spectrometry and Synthesis of Triisopropylkwakhurin

Kwakhurin (5), a characteristic isoflavone component of Pueraria mirifica which has been used in folk medicine as kwao keur for rejuvenating purpose, was structurally approached by 2D-NMR experiments. Furthermore, the synthesis of kwakhurin (5) was attempted starting from the methyl ketone (12). Thus, deoxybenzoin derivative (22) was prepared by Friedel-Crafts acylation after protection of the phenolic function with a triisopropyl group. Modification of the substituents, O-prenylation, prenyl 1,3-rearrangement, and O-methylation afforded kwakhurin triisopropyl ether (38).

A facile synthesis of benzo[b]thiophene derivatives

Lithiation of S-(2-methylphenyl) N,N,N',N'-tetramethylphosphorodiamidothioate with sec-BuLi at -105° gave the corresponding benzylic anion which was acylated with various aromatic esters to give various deoxybenzoin derivatives in moderate to high yields. Acidic treatment of these products in refluxing formic acid gave 2-arylbenzo[b]thiophene derivatives. 2-Methylbenzo[b]thiophene and benzo[b]thiophen-2(3H)-one were also prepared using the similar procedure.

A short and convergent synthesis of the phytoalexins vignafuran, 6-demethylvignafuran, and moracin M via directed lithiation reaction.

2-Methyl-5-(tert-butyldimethylsilyloxy)phenyl N, N, N', N'-tetramethylphosphorodiamidate was lithiated with sec-BuLi in the presence of N, N, N', N'-tetramethylethylenediamine at -105°C to generate the corresponding benzylic anion. This benzylic anion was reacted with various methyl benzoates to provide deoxybenzoin derivatives which, without purification, were treated with formic acid to give 2-aryl-6-hydroxybenzo[b]furans. The utility of this strategy has been demonstrated by its application to the short synthesis of phytoalexins, such as vignafuran, 6-demethylvignafuran, and moracin M.

Lithiation of ortho-tolyl tetramethylphosphorodiamidates. A facile synthessis of 2-arylbenzofurans including neolignan, carinatin.

ortho-Tolyl tetramethylphosphorodiamidates were lithiated with sec-BuLi at -105°C to give corresponding benzylic lithio species which underwent reaction with electrophiles. When benzoates were used as electrophiles, deoxybenzoin derivatives were obtained. Acidic treatment of these products in refluxing formic acid gave 2-arylbenzofurans. The neolignan, carinatin, was successfully synthesized using this methodology.