Next Article in Journal
Antimicrobial Clothing Based on Electrospun Fibers with ZnO Nanoparticles
Next Article in Special Issue
The Road to Malignant Cell Transformation after Particulate Matter Exposure: From Oxidative Stress to Genotoxicity
Previous Article in Journal
Differential Regulation of Innate Lymphoid Cells in Human and Murine Oral Squamous Cell Carcinoma
Previous Article in Special Issue
Increased Oxidative Stress Markers in Acute Ischemic Stroke Patients Treated with Thrombolytics
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
IJMS
Volume 24
Issue 2
10.3390/ijms24021623
ijms-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Synthesis and Antimicrobial Activity of the Pathogenic E. coli Strains of p-Quinols: Additive Effects of Copper-Catalyzed Addition of Aryl Boronic Acid to Benzoquinones

by
Dominik Koszelewski
1,*,
Paweł Kowalczyk
2,*,
Jan Samsonowicz-Górski
1,
Anastasiia Hrunyk
1,
Anna Brodzka
1,
Justyna Łęcka
1,
Karol Kramkowski
3 and
Ryszard Ostaszewski
1
1
Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland
2
Department of Animal Nutrition, The Kielanowski Institute of Animal Physiology and Nutrition, Polish Academy of Sciences, Instytucka 3, 05-110 Jabłonna, Poland
3
Department of Physical Chemistry, Medical University of Bialystok, Kilińskiego 1 Str., 15-089 Białystok, Poland
*
Authors to whom correspondence should be addressed.
Int. J. Mol. Sci. 2023, 24(2), 1623; https://doi.org/10.3390/ijms24021623
Submission received: 16 December 2022 / Revised: 30 December 2022 / Accepted: 10 January 2023 / Published: 13 January 2023
(This article belongs to the Special Issue Role of Redox Homeostasis and Oxidative Stress in Human Health)
Browse Figures
Review Reports Versions Notes

Abstract

:
A mild and efficient protocol for the synthesis of p-quinols under aqueous conditions was developed. The pivotal role of additives in the copper-catalyzed addition of aryl boronic and heteroaryl boronic acids to benzoquinones was observed. It was found that polyvinylpyrrolidone (PVP) was the most efficient additive used for the studied reaction. The noteworthy advantages of this procedure include its broad substrate scope, high yields up to 91%, atom economy, and usage of readily available starting materials. Another benefit of this method is the reusability of the catalytic system up to four times. Further, the obtained p-quinols were characterized on the basis of their antimicrobial activities against E. coli. Antimicrobial activity was further compared with the corresponding 4-benzoquinones and 4-hydroquinones. Among tested compounds, seven derivatives showed an antimicrobial activity profile similar to that observed for commonly used antibiotics such as ciprofloxacin, bleomycin, and cloxacillin. In addition, the obtained p-quinols constitute a suitable platform for further modifications, allowing for a convenient change in their biological activity profile.

1. Introduction

p-Quinol skeletons are frequently found in many bioactive natural products [1,2,3,4], and they also serve as useful synthetic building blocks [5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27] (Scheme 1). Moreover, p-quinol glycosides are known from analgesic activities [27].
The examination of the toxic effect of 1,4-cyclohexadienones on bacterial cells can provide appropriate antimicrobial agents against microbial clinical pathogens [28,29,30,31,32,33] (Figure 1). The aim of the present study is the development of an efficient method of isolating p-quinol derivatives with aryl and heteroaryl groups and their validation against model pathogenic strains of Escherichia coli K12 (with native lipopolysaccharide (LPS) in its structure) and R2–R4 (LPS of different lengths in its structure). General methods of obtaining p-quinols are based on the dearomatization of para-substituted phenols via oxidation using hypervalent iodine reagents [34]. However, this approach often suffers from low yields because of competitive oligomerization, especially in the case of oxidation of 4-arylphenols [35]. Thus, the development of a new method to overcome these limitations is of great importance [35,36,37,38,39].

2. Results and Discussion

2.1. Chemistry

Recently, we have developed a sustainable method for the synthesis of p-quinols based on the copper-catalyzed addition of phenylboronic acid to quinone, leading to a target product formation under aqueous conditions [40]. However, desired products were obtained with moderate yields. Additionally, the formation of side products hampered product purification. Therefore, the previously developed method is characterized by low atom economy [41,42,43,44,45,46,47].
As a continuation of our research on the search for new catalytic activities of copper salts, we focused our efforts on elaborating an efficient and sustainable method of obtaining desired p-quinols (Scheme 1). Based on our recent findings regarding the activity of copper (I) iodide [40], the model addition reaction of phenylboronic acid (1 mmol) and benzoquinone (1 mmol) was conducted in distilled water at 20 °C under atmospheric pressure (Scheme 1, Table 1, entry 1). As a result, the mixture of products 1 and 15 with 51% and 9% yields, respectively (Scheme 1, Table 1, entry 1), was obtained. In order to discover more reusable catalysts and to enhance the reaction efficiency, solid supported catalysts have been developed for catalytic applications [48]. In addition to this, Cu(I) species immobilized onto various supports, such as silica [49], zeolites [50], activated charcoal [51], and amine functionalized polymers [52] have been reported recently. The character of supporting materials on which nanoparticles are stabilized plays a crucial role in catalysis as it provides a highly active catalyst surface, which increases the reaction rate. Inspired by the work of Liu et al. [53], an anion exchange resin (Amberlite IRA 400) was employed as the additive, resulting in target product 1 with an enhanced yield (Table 1, entry 2). Encouraged by this result, various different adsorbents including ionic polymers having quaternary ammonium were tested (Table 1). Further improvement in the reaction yield was achieved by the application of montmorillonite, producing target product 1 with 64% yield. It should be mention that the formation of 1,4-addition product 15 was not observed (Table 1, entry 3). An application of basic amberylst [54] resulted in the formation of target product 1 with a reduced reaction yield (18%, Table 1, entry 4), while the application of quaternary ammonium based Dowex-1 provided p-quinol 1 with 68% (Table 1, entry 5). Ionic polymers like Dowex-1 were already found to be efficient support for CuI catalysts in Huisgen’s 1,3-dipolar cycloaddition [55]. No impact on the reaction yield was observed in the case of using silica gel or aluminum oxide (Table 1, entries 6 and 7). Chavan and his group demonstrated cellulose supported cuprous iodide as an efficient catalyst in the click synthesis of 1,4-disubstituted 1,2,3-triazoles [56]; however, we have not observed any pivotal impact of this additive on the studied reaction (Table 1, entry 8).
Metal organic frameworks (MOFs) have been effectively used as heterogeneous catalysts improving efficiency and selectivity of various reactions. The specific porous structure of MOF containing organic and inorganic active sites is a useful and effective alternative to heterogeneous catalysts [57,58]. Two MOFs prepared in accordance with the literature procedures [59,60] were tested in the model reaction. However, a product was obtained with a moderate yield up to 42% (Table 1, entries 9 and 10). On the other hand, the advantage of MOFs was their easy separation from the reaction mixture and reusability. The MOF-1 catalyst was used three times. The yield after the third cycle was 27%. The catalyst was isolated by filtration on a silica sinter. The decrease in yield could be related to the physical loss of the catalyst during separation from the reaction mixture. Colloidal synthesis offers a route to nanoparticles (NPs) with controlled composition and structural features. Polyvinylpyrrolidone (PVP) can serve as a surface stabilizer, growth modifier, nanoparticle dispersant, and reducing agent [61]. High surface-to-volume ratios make metal colloids promising candidates for active catalysts [62]. Copper-PVP composites have been found to be efficient catalysts for click reactions [63,64,65]. Among three different PVPs, an application of this with 3500 average molecular weight provided target product 1 with 84% yield. Moreover, for each type of used PVP, only a formation of 1,2-addition product 1 was observed (Table 1, entries 11–13). An increased amount of the used PVP, 15 mol% and 20 mol%, did not affect the reaction yield (Table 1, entries 14 and 15). Next, the impact of temperature on the model reaction was studied. When the reaction was conducted at 30 °C, the yield increased to 89%. However, the further elevation of temperature led to a decrease in yield, which may be explained by the changes in the colloidal structure of the catalyst (Table 1, entries 16-17). The application of methanol as a reaction medium, which was found previously [40] to be suitable for the studied reaction, resulted in target product 1 with reduced yield (Table 1, entry 18, Figure 2).
The model reaction was carried out under the optimized procedure. Formed product 1 was separated by extraction with EtOAc, followed by purification using column chromatography. The remaining aqueous phase containing the CuI-PVP catalytic system was employed for another run with the fresh portion of substrates (Figure 3). Due to the possibility of repeated use of the reaction medium containing the catalyst, the E-factor for the developed procedure is lower than that for the reaction with copper iodide alone.
Finally, the elaborated protocol was applied for the synthesis of the series of p-quinols 2–10 with good to very high yields for various boronic acids (Figure 4). In case of using 2-methyl-1,4-benzoquinone as the substrate, only one of two possible regioisomers was obtained with 82% (p-quinol 10). The developed protocols were also revealed to be efficient for heterocyclic boronic acids, resulting in the formation of products 8 and 9 with good yield. Principally, with the exception of compound 6, all others were obtained with much higher yields compared to the reaction carried out under conditions without PVP presented in the previous work [40].

2.2. Cytotoxic Studies of the Library of p-Quinols 1–10, and Parent Benzo- and Hydroquinones 11–14

The toxic effect on bacterial cells was studied after the analysis of the MIC and MBC test for all 14 tested compounds (Figure 4 and Figure 5). The MIC values were observed in the range of 0.2–1.4 µg/mL and 2–82 µg/mL for MBC values in the analyzed model strains K12, R2, R3, and R4 (Figure 6 and Figure 7), which had specific functional groups in the structure of the 4-hydroxycyclohexa-2,5-dienones.

2.3. Analysis of Bacterial DNA Isolated from E. coli R2–R4 Strains Modified with Tested p-Quinols

The obtained MIC values, as well as our previous studies with various types of the analyzed compounds [65,66,67,68,69,70,71,72,73,74,75,76,77,78,79,80], (Figure 8) indicate that p-quinols show a strong toxic effect on the analyzed bacterial model strains. Based on the MIC and MBC values, the analyzed compounds 5, 7, 10, and 11 were selected for further analyses (on the basis of their highest biological activity similar to that of antibiotics) and their values were selected for further studies related to the analysis of oxidative stress in the cell by modifying them with the bacterial DNA obtained from the analyzed strains. On the other hand, compounds numbered 1–4, 6, 8, 9, and 12–14 showed higher activity than selected compounds 5, 7, 10, and 11, with activity similar to the biological activity of antibiotics (see Figures S2–S25 in Supplementary Materials, Table 2).
The conducted research proved that the analyzed and newly synthesized compounds have the potential (further functionalization) to find a new innovative application in the future after their more in-depth examination on e.g. specific cell cultures as potential “replacements” of currently used antibiotics commonly used in hospital and clinical infections (Figure 9).
It is noteworthy that both the hydrophilic compound 5 containing two methoxy groups in its structure as well as the lipophilic p-quinol 7 show the highest antimicrobial activity. This may indicate a different mechanism of action of these compounds on selected strains of E. coli (Figure 10 and Figure 11)A significant effect of the methyl group present in the 2-position of the p-quinol ring on the increased antimicrobial activity was also noted [67,68,69,70,71,72,73,74,75,76,77,78,79,80] (Figure 4). Dysfunction of bacterial membranes containing different lengths of LPS in model bacterial strains is an ideal model to assess the effectiveness of these compounds in relation to the antibiotics used [67,68,69,70,71,72,73,74,75,76].

3. Materials and Methods

3.1. Microorganisms and Media

The entire methodology and all materials and media used are detailed in previous work [67,68,69,70,71,72,73,74,75,76], and data were analyzed by the Tukey test indicated by (p < 0.05): * p < 0.05, ** p < 0.1, *** p < 0.01.

3.2. Minimum Inhibitory Concentration (MIC) and Minimum Bactericidal Concentration (MBC)

The MIC was estimated by a microtiter plate method using sterile 48 or 96-well plates [69,70,71,72,73,74,75,76,77,78]. The mother liquor was prepared in DMSO at a concentration of 20 mg/mL−1. Samples at a given concentration were prepared by diluting the mother liquor with distilled water.

3.3. Chemicals

The chemistry used for the research came from Sigma-Aldrich, Saint Louis, MI, USA.

3.4. General Procedure for the Synthesis of p-Quinols

Quinone derivative (0.4 mmol), boronic acid derivative (0.4 mmol), and catalyst (10 mol%) together with PVP (10 mol%) were stirred in distilled water (2 mL) at room temperature.
4-Hydroxy-4-phenyl-cyclohexa-2,5-dienone (1). Compound 1 was obtained according to the general method with 89% yield (166 mg, 0.89 mmol) as a white solid; m.p. 103–104 °C [Lit. m.p. 102–103 °C; [81]; 1H NMR (400 MHz, CDCl3) δ 7.55–7.43 (m, 2H), 7.43–7.28 (m, 3H), 6.90 (d, J = 10.1 Hz, 2H), 6.22 (d, J = 10.1 Hz, 2H), 2.71 (s, 1H); 13C NMR (100 MHz, CDCl3) δ 185.7, 150.8, 138.7, 128.9, 128.4, 126.8, 125.2, 71.0. NMR data were in accordance with those reported in the literature [82].
4-Hydroxy-4-(4′-methyl)-phenyl-cyclohexa-2,5-dienone (2). Compound 2 was obtained according to the general method with 72% yield (144 mg, 0.72 mmol) as a white solid; m.p. 134–137 °C, Lit. m.p. 134–137 °C [83] 1H NMR (400 MHz, CDCl3) δ 7.36 (d, J = 8.3 Hz, 2H), 7.21–7.13 (m, 2H), 6.88 (d, J = 10.0 Hz, 2H), 6.20 (d, J = 10.0 Hz, 2H), 2.64 (s, 1H), 2.35 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 185.7, 150.9, 138.3, 135.7, 129.6, 126.7, 125.1, 70.9, 21.0. NMR data were in accordance with those reported in the literature [84].
4-Hydroxy-4-(4′-chloro)-phenyl-cyclohexa-2,5-dienone (3). Compound 3 was obtained according to the general method with 64% yield (141 mg, 0.64 mmol) as a white solid; m.p. 170–172 °C, Lit. m.p. 171–172 [85]; 1H NMR (400 MHz, CDCl3) δ 7.41 (d, J = 8.7 Hz, 2H), 7.34 (d, J = 8.7 Hz, 2H), 6.85 (d, J = 10.1 Hz, 2H), 6.22 (d, J = 10.1 Hz, 2H), 2.74 (s, 1H); 13C NMR (100 MHz, CDCl3) δ 185.4, 150.3, 137.2, 134.4, 130.4, 127.0, 126.8, 70.6. NMR data were in accordance with those reported in the literature [40].
4-Hydroxy-4-(4′-formyl)-phenyl-cyclohexa-2,5-dienone (4). Compound 4 was obtained according to the general method with 31% yield (66 mg, 0.31 mmol) as a white solid; m.p. 158–159 °C; 1H NMR (400 MHz, CDCl3) δ 10.01 (s, 1H), 7.89 (d, J = 8.6 Hz, 2H), 7.66 (d, J = 8.3 Hz, 2H), 6.87 (d, J = 10.1 Hz, 2H), 6.28 (d, J = 10.1 Hz, 2H), 2.84 (s, 1H); 13C NMR (100 MHz, CDCl3) δ 191.6, 185.2, 149.7, 145.2, 136.2, 130.2, 127.5, 126.1, 71.0. NMR data were in accordance with those reported in the literature [40].
4-(3,4-Dimethoxyphenyl)-4-hydroxycyclohexa-2,5-dien-1-one (5). Compound 5 was obtained according to the general method with 43% yield (106 mg, 0.43 mmol) as a white solid; m.p. 164–166 °C; 1H NMR (400 MHz, CDCl3) δ 7.43 (d, J = 8.6 Hz, 2H), 7.11–7.03 (m, 2H), 6.92 (d, J = 8.2 Hz, 1H), 6.89 (d, J = 8.6 Hz, 2H), 3.93 (s, 3H), 3.91 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 185.2, 154.8, 149.1, 134.0, 128.0, 118.9, 115.6, 111.6, 110.3, 69.7, 56.0, 55.9. NMR data were in accordance with those reported in the literature [40].
4-Hydroxy-4-(4′-hydroxymethylphenyl)phenyl-cyclohexa-2,5-dienone (6). Compound 6 was obtained according to the general method with 29% yield (63 mg, 0.29 mmol) as a white solid; m.p. 181–182 °C; 1H NMR (500 MHz, Acetone-d6) δ 8.20 (s, 1H), 7.30 (d, J = 8.6 Hz, 2H), 6.92–6.78 (m, 6H), 4.57 (s, 2H); 13C NMR (126 MHz, Acetone) δ 186.2, 158.6, 154.5, 150.2, 137.3, 128.9, 121.5, 117.8, 117.0, 69.9, 64.2. NMR data were in accordance with those reported in the literature [40].
4-Hydroxy-4-(4′-biphenyl)phenyl-cyclohexa-2,5-dienone (7). Compound 7 was obtained according to the general method with 54% yield (142 mg, 0.54 mmol) as a white solid; m.p. 146–148 °C; 1H NMR (400 MHz, CDCl3) δ 7.59–7.48 (m, 4H), 7.48–7.37 (m, 2H), 7.37–7.27 (m, 1H), 7.03–6.93 (m, 3H), 6.84 (d, J = 8.9 Hz, 2H), 4.80 (s, 1H); 13C NMR (101 MHz, CDCl3) δ 185.0, 158.0, 151.8, 150.2, 140.6, 135.6, 128.7, 128.3, 126.9, 126.8, 121.0, 117.8, 116.4, 70.4. NMR data were in accordance with those reported in the literature [86].
4-Hydroxy-4-(thiophen-3-yl) phenyl-cyclohexa-2,5-dienone (8). Compound 8 was obtained according to the general method with 76% yield (204 mg, 0.76 mmol) as a white solid; m.p. 138–139 °C; 1H NMR (400 MHz, CDCl3) δ 7.41–7.21 (m, 2H), 7.09–6.89 (m, 3H), 6.26–6.04 (m, 2H), 3.64 (s, 1H); 13C NMR (100 MHz, CDCl3) δ 185.9, 150.7, 140.3, 126.9, 126.5, 125.2, 122.0, 69.5.; HRMS calculated for C10H8O2S [M+H]+: 193.0323, found: 193.0320.
4-Hydroxy-4-(furan-3-yl) phenyl-cyclohexa-2,5-dienone (9). Compound 9 was obtained according to the general method with 69% yield (174 mg, 0.69 mmol) as a white solid; m.p. 131–133 °C; 1H NMR (400 MHz, CDCl3) δ 7.44 (d, J = 24.8 Hz, 2H), 6.95 (d, J = 10.1 Hz, 2H), 6.34 (d, J = 1.0 Hz, 1H), 6.19 (d, J = 10.2 Hz, 2H), 2.66 (s, 1H); 13C NMR (100 MHz, CDCl3) δ 149.7, 143.9, 139.6, 127.0, 125.8, 108.1, 66.8.; HRMS calculated for C10H8O3 [M+H]+: 177.0552, found: 177.0555.
4-Hydroxy-2-methyl-4-phenyl-2,5-cyclohexadienone (10). Compound 10 was obtained according to the general method with 82% yield (164 mg, 0.82 mmol) as a white solid; m.p. 76–77 °C [Lit. m.p. 73–75 °C (diethyl ether, hexane) [86]; 1H NMR (400 MHz, CDCl3) δ 7.47–7.25 (m, 5H), 6.87–6.77 (m, 1H), 6.19–6.03 (m, 2H), 2.99 (s, 1H), 1.83 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 186.7, 161.7, 151.9, 138.5, 128.7, 128.0, 126.3, 125.7, 125.2, 73.2, 18.4. NMR data were in accordance with those reported in the literature [87].
2-Phenyl-1,4-benzoquinone (15). White solid; m.p. 118–119 °C [Lit. m.p. 117–118 [88]; 1H NMR (400 MHz, CDCl3) δ 7.55–7.38 (m, 5H), 6.90–6.78 (m, 3H); 13C NMR (100 MHz, CDCl3) δ 187.5, 186.6, 145.9, 137.0, 136.2, 132.6, 130.1, 129.2, 128.5. NMR data were in accordance with those reported in the literature [88].

3.5. Preparation of Copper–PVP Colloids in Water

Colloidal solution of copper PVP was prepared by vigorously stirring for 30 minutes at room temperature a mixture of CuI (8 mg, 0.04 mmol) and PVP (10%mol) in distilled water (4 mL).

4. Conclusions

The novel efficient protocol for obtaining p-Quinols was developed. The crucial role of additives in the reaction course was shown. The pivotal role of polyvinylpyrrolidone (PVP) in a colloidal catalyst system was revealed, and it was applied for the synthesis of various p-Quinols with very good yields and excellent chemo- and regioselctivity. Moreover, the developed colloidal system can be reused several times, which significantly reduces the overall cost of the synthesis.

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/ijms24021623/s1.

Author Contributions

Conceptualization, P.K. and D.K.; methodology, P.K., D.K., J.S.-G., A.H., A.B., J.Ł., K.K. and R.O.; investigation, P.K. and D.K.; resources, P.K.; data curation, K.K. and A.B.; writing—original draft preparation, P.K., R.O. and D.K; writing—review and editing, D.K., R.O. and P.K.; supervision, P.K. All authors have read and agreed to the published version of the manuscript.

Funding

This work was supported by a grant from the Medical University of Białystok Grant of National Science Center Opus 22 Nr 2021/43/B/NZ7/01903 and by National Science Center, Poland project OPUS No. 2019/33/B/ST4/01118. We would like to acknowledge COST Action CA18224 “Green Chemical Engineering Network towards upscaling sustainable processes”.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

On request of those interested.

Acknowledgments

The authors thank Jolanta Łukasiewicz from Ludwik Hirszfeld Institute of Immunology and Experimental Therapy (Polish Academy of Sciences) for providing the strains of E. coli. We would like to thank Agata Koszelewska for her help in editing schemes and figures.

Conflicts of Interest

The authors declare no conflict of interest.

Abbreviations

MICminimum inhibitory concentration
MBCminimum bactericidal concentration
Ocopen circle
Ccccovalently closed circle
BERbase excision repair
FpgDNA-formamidopyrimidine glycosylase

References

  1. Prestinaci, F.; Pezzotti, P.; Pantosti, A. Antimicrobial resistance: A global multifaceted phenomenon. Pathog. Glob. Health 2015, 109, 309–318. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  2. Abe, N.; Sugimoto, O.; Tanji, K.; Hirota, A. Identification of the Quinol Metabolite “Sorbicillinol”, a Key Intermediate Postulated in Bisorbicillinoid Biosynthesis. J. Am. Chem. Soc. 2000, 122, 12606–12607. [Google Scholar] [CrossRef]
  3. Urban, S.; Blunt, J.W.; Munro, M.H.G. Coproverdine, a Novel, Cytotoxic Marine Alkaloid from a New Zealand Ascidian. J. Nat. Prod. 2002, 65, 1371–1373. [Google Scholar] [CrossRef] [Green Version]
  4. Chan, H.-H.; Hwang, T.-L.; Thang, T.D.; Leu, Y.-L.; Kuo, P.-C.; Nguyet, B.T.M.; Dai, D.N.; Wu, T.-S. Isolation and Synthesis of Melodamide A, a New Anti-inflammatory Phenolic Amide from the Leaves of Melodorum fruticosum. Planta Med. 2013, 79, 288–294. [Google Scholar] [CrossRef] [Green Version]
  5. Magdziak, D.; Meek, S.J.; Pettus, T.R.R. Cyclohexadienone ketals and quinols: Four building blocks potentially useful for enantioselective synthesis. Chem. Rev. 2004, 104, 1383–1429. [Google Scholar] [CrossRef] [PubMed]
  6. Marco-Contelles, J.; Molina, M.T.; Anjum, S. Naturally Occurring Cyclohexane Epoxides:  Sources, Biological Activities, and Synthesis. Chem. Rev. 2004, 104, 2857–2900. [Google Scholar] [CrossRef]
  7. You, Z.; Hoveyda, A.H.; Snapper, M.L. Catalytic Enantioselective Silylation of Acyclic and Cyclic Triols: Application to Total Syntheses of Cleroindicins D, F, and C. Angew. Chem. Int. Ed. 2009, 48, 547–558. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  8. Tello-Aburto, R.; Kalstabakken, K.A.; Volp, K.A.; Harned, A.M. Regioselective and stereoselective cyclizations of cyclohexadienones tethered to active methylene groups. Org. Biomol. Chem. 2011, 9, 7849–7859. [Google Scholar] [CrossRef]
  9. Zhang, J.; Wu, J.; Yin, Z.; Zeng, H.; Khanna, K.; Huc, C.; Zheng, S. An expedient stereoselective and chemoselective synthesis of bicyclic oxazolidinones from quinols and isocyanates. Org. Biomol. Chem. 2013, 11, 2939–2942. [Google Scholar] [CrossRef]
  10. Xie, L.; Dong, S.; Zhang, Q.; Feng, X.; Liu, X. Asymmetric construction of dihydrobenzofuran- 2,5-dione derivatives via desymmetrization of p-quinols with azlactones. Chem. Commun. 2019, 55, 87–90. [Google Scholar] [CrossRef]
  11. Kitson, R.R.A.; Taylor, R.J.K.; Wood, J.L. A One-Pot, Base-Free Annelation Approach to r-Alkylidene-γ-butyrolactones. Org. Lett. 2009, 11, 5338–5341. [Google Scholar] [CrossRef]
  12. Moon, N.G.; Harned, A.M. A concise synthetic route to the stereotetrad core of the briarane diterpenoids. Org. Lett. 2015, 17, 2218–2221. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  13. García-García, C.; Ortiz-Rojano, L.; Álvarez, S.; Álvarez, R.; Ribagorda, M.; Carreño, M.C. Friedel–Crafts Alkylation of Indoles with p-Quinols: The Role of Hydrogen Bonding of Water for the Desymmetrization of the Cyclohexadienone System. Org. Lett. 2016, 18, 2224–2227. [Google Scholar] [CrossRef] [PubMed]
  14. Imbos, R.; Minnaard, A.J.; Feringa, B.L. A Highly Enantioselective Intramolecular Heck Reaction with a Monodentate Ligand. J. Am. Chem. Soc. 2002, 124, 184–185. [Google Scholar] [CrossRef] [Green Version]
  15. Liu, Q.; Rovis, T. Asymmetric Synthesis of Hydrobenzofuranones via Desymmetrization of Cyclohexadienones Using the Intramolecular Stetter Reaction. J. Am. Chem. Soc. 2006, 128, 2552–2553. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  16. Xing, J.-J.; Gao, Y.-N.; Shi, M. Phosphine-Initiated Cascade Annulation of β′-Acetoxy Allenoate and p-Quinols: Access to Ring Fused Hexahydroindeno Furan Derivatives. Adv. Synth. Catal. 2018, 360, 2552–2559. [Google Scholar] [CrossRef]
  17. Zhao, F.; Li, N.; Zhu, Y.-F.; Han, Z.-Y. Enantioselective Construction of Functionalized Tetrahydrocarbazoles Enabled by Asymmetric Relay Catalysis of Gold Complex and Chiral Brønsted Acid. Org. Lett. 2016, 18, 1506–1509. [Google Scholar] [CrossRef]
  18. Li, F.; Wang, J.; Xu, M.; Zhao, X.; Zhou, X.; Zhao, W.; Liu, L. Catalytic stereoselective cascade reactions of quinols with trifluoromethyl ketones: Direct access to CF3-containing 1,3-dioxolanes. Org. Biomol. Chem. 2016, 14, 3981–3988. [Google Scholar] [CrossRef]
  19. Berry, J.M.; Bradshaw, T.D.; Fichtner, I.; Ren, R.; Schwalbe, C.H.; Wells, G.; Chew, E.H.; Stevens, M.F.G.; Westwell, A.D. Quinols as Novel Therapeutic Agents. 2.1 4-(1-Arylsulfonylindol-2-yl)-4-hydroxycyclohexa-2,5-dien-1-ones and Related. Agents as Potent and Selective Antitumor Agents. J. Med. Chem. 2005, 48, 639–644. [Google Scholar] [CrossRef]
  20. Bradshaw, T.D.; Matthews, C.S.; Cookson, J.; Chew, E.H.; Shah, M.; Bailey, K.; Monks, A.; Harris, E.; Westwell, A.D.; Wells, G.; et al. Elucidation of Thioredoxin as a Molecular Target for Antitumor Quinols. Cancer Res. 2005, 65, 3911–3919. [Google Scholar] [CrossRef]
  21. Wells, G.; Berry, J.M.; Bradshaw, T.D.; Burger, A.M.; Seaton, A.; Wang, B.; Westwell, A.D.; Stevens, M.F.G. 4-Substituted 4-Hydroxycyclohexa-2,5-dien-1-ones with Selective Activities against Colon and Renal Cancer Cell Lines. J. Med. Chem. 2003, 46, 532–541. [Google Scholar] [CrossRef] [PubMed]
  22. Jones, D.T.; Pugh, C.W.; Wigfield, S.; Stevens, M.F.G.; Harris, A.L. Novel Thioredoxin Inhibitors Paradoxically Increase Hypoxia-Inducible Factor-A Expression but Decrease Functional Transcriptional Activity, DNABinding, and Degradation. Clin. Cancer Res. 2006, 12, 5384–5394. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  23. Morais, T.R.; Romoff, P.; Fávero, O.A.; Reimão, J.Q.; Lourenço, W.C.; Tempone, A.G.; Hristov, A.D.; Di Santi, S.M.; Lago, J.H.G.; Sartorelli, P.; et al. Anti-malarial, anti-trypanosomal, and anti-leishmanial activities of jacaranone isolated from Pentacalia desiderabilis (Vell.) Cuatrec. (Asteraceae). Parasitol. Res. 2012, 110, 95–101. [Google Scholar] [CrossRef] [PubMed]
  24. König, J.; Wyllie, S.; Wells, G.; Stevens, M.F.; Wyatt, P.G.; Fairlamb, A.H. Antitumor Quinol PMX464 Is a Cytocidal Anti-trypanosomal Inhibitor Targeting Trypanothione Metabolism. J. Biol. Chem. 2011, 286, 8523–8533. [Google Scholar] [CrossRef] [Green Version]
  25. Capes, A.; Patterson, S.; Wyllie, S.; Hallyburton, I.; Collie, I.T.; McCarroll, A.J.; Stevens, M.F.G.; Frearson, J.A.; Wyatt, P.G.; Fairlamb, A.H.; et al. Quinol derivatives as potential trypanocidal agents. Bioorg. Med. Chem. 2012, 20, 1607–1615. [Google Scholar] [CrossRef] [Green Version]
  26. Lajide, L.; Escoubas, P.; Mizutani, J. Cyclohexadienones-insect growth inhibitors from the foliar surface and tissue extracts of Senecio cannabifolius. Experientia 1996, 52, 259–263. [Google Scholar] [CrossRef]
  27. Lia, H.-X.; Xiaoa, C.-J.; Wangb, M.; Cuib, S.-J.; Lia, H.-F.; Wanga, K.-L.; Donga, X.; Jiang, B. Four new phenylethanoid glycosides from Ternstroemia gymnanthera and their analgesic activities. Phytochem. Lett. 2019, 34, 25–29. [Google Scholar] [CrossRef]
  28. Abraham, I.; Joshi, R.; Pardasani, P.; Pardasani, R.T. Recent Advances in 1,4-Benzoquinone Chemistry. J. Braz. Chem. Soc. 2011, 22, 385–421. [Google Scholar] [CrossRef] [Green Version]
  29. Singh, N.; Mishra, B.B.; Bajpai, S.; Singh, R.K.; Tiwari, V.K. Natural product based leads to fight against leishmaniasis. Bioorg. Med. Chem. 2014, 22, 18–45. [Google Scholar] [CrossRef]
  30. Drewes, S.E.; Khan, F.; van Vuuren, S.F.; Viljoen, A.M. Simple 1,4-benzoquinones with antibacterial activity from stems and leaves of Gunnera perpensa. Phytochemistry 2005, 66, 1812–1816. [Google Scholar] [CrossRef]
  31. Kim, M.-H.; Jo, S.-H.; Ha, K.-S.; Song, J.-H.; Jang, H.-D.; Kwon, Y.-I. Antimicrobial Activities of 1,4-Benzoquinones and Wheat Germ Extract. J. Microbiol. Biotechnol. 2010, 20, 1204–1209. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  32. Carcamo-Noriegaa, E.N.; Sathyamoorthib, S.; Banerjeeb, S.; Gnanamanib, E.; Mendoza-Trujillod, M.; Mata-Espinosad, D.; Hernández-Pandod, R.; Veytia-Buchelia, J.I.; Possania, L.D.; Zare, R.N. 1,4-Benzoquinone antimicrobial agents against Staphylococcus aureus and Mycobacterium tuberculosis derived from scorpion venom. Proc. Natl. Acad. Sci. USA 2019, 116, 12642–12647. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  33. Ma, C.; He, N.; Zhao, Y.; Xia, D.; Wei, J.; Kang, W. Antimicrobial Mechanism of Hydroquinone. Appl. Biochem. Biotechnol. 2019, 189, 1291–1303. [Google Scholar] [CrossRef] [PubMed]
  34. Yakura, T.; Omoto, M. Efficient Synthesis of P-Quinols Using Catalytic Hypervalent Iodine Oxidation of 4-arylphenols with 4-iodophenoxyacetic Acid and Oxone. Chem. Pharm. Bull. 2009, 57, 643–645. [Google Scholar] [CrossRef] [Green Version]
  35. Felpin, F.-X. Oxidation of 4-arylphenol trimethylsilyl ethers to p-arylquinols using hypervalent iodine(III) reagents. Tetrahedron Lett. 2007, 48, 409–412. [Google Scholar] [CrossRef]
  36. Fischer, A.; Henderson, G.N. Reactions of organolithium reagents with p-benzoquinones and cyclohexadienones. Synthesis of 4-alkyl-4-hydroxycyclohexa-2,5-dien-1-ones and 1,4-dialkylcyclohexa-2,5-diene-1,4-diols. Tetrahedron Lett. 1980, 21, 701–704. [Google Scholar] [CrossRef]
  37. Ghandi, M.; Shahidzadeh, M. Experimental and semiemprical stud-ies of chemical reactivity of dialkylcadmium reagents addition to α,β-enones. J. Organometal. Chem. 2006, 691, 4918–4925. [Google Scholar] [CrossRef]
  38. Muthusamy, S.; Krishnamurthi, J. Multicomponent reactions involving p-benzoquinones, diazo esters, titanium(IV) isopropoxide and alcohol in the presence of rhodium(II) acetate as catalyst. Tetrahedron Lett. 2007, 48, 6692–6695. [Google Scholar] [CrossRef]
  39. Krause, K.P.; Kayser, O.; Mäder, K.; Gust, R.; Müller, R.H. Heavy metal contamination of nanosuspensions produced by high-pressure homogenisation. Int. J. Pharmaceut. 2000, 196, 169–172. [Google Scholar] [CrossRef]
  40. Koszelewski, D.; Paprocki, D.; Brodzka, A.; Kęciek, A.; Wilk, M.; Ostaszewski, R. The sustainable copper-catalyzed direct formation of highly functionalized p-quinols in water. Sustain. Chem. Pharm. 2022, 25, 100576. [Google Scholar] [CrossRef]
  41. Ranu, B.C.; Dey, R.; Chatterjee, T.; Ahammed, S. Copper Nanoparticle-Catalyzed Carbon-Carbon and Carbon-Heteroatom Bond Formation with a Greener Perspective. ChemSusChem 2012, 5, 22–44. [Google Scholar] [CrossRef] [PubMed]
  42. Iwamatsu, S.-i.; Matsubara, K.; Nagashima, H. Synthetic Studies of cis-3a-Aryloctahydroindole Derivatives by Copper-Catalyzed Cyclization of N-Allyltrichloroacetamides:  Facile Construction of Benzylic Quaternary Carbons by Carbon−Carbon Bond-Forming Reactions. J. Org. Chem. 1999, 64, 9625–9631. [Google Scholar] [CrossRef]
  43. Shilpa, T.; Neetha, M.; Anilkumara, G. Recent Trends and Prospects in the Copper-Catalysed “on Water” Reactions. Adv. Synth. Catal. 2021, 363, 1559–1582. [Google Scholar] [CrossRef]
  44. Villalobos, J.M.; Srogl, J.; Liebeskind, L.S. A New Paradigm for Carbon−Carbon Bond Formation:  Aerobic, Copper-Templated Cross-Coupling. J. Am. Chem. Soc. 2007, 129, 15734–15735. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  45. Prokopcová, H.; Kappe, C.O. Palladium(0)-Catalyzed, Copper(I)-Mediated Coupling of Boronic Acids with Cyclic Thioamides. Selective Carbon−Carbon Bond Formation for the Functionalization of Heterocycles. J. Org. Chem. 2007, 72, 4440–4448. [Google Scholar] [CrossRef] [PubMed]
  46. Ghasemi, N.; Yavari, A.; Bahadorikhalili, S.; Moazzam, A.; Hosseini, S.; Larijani, B.; Iraji, A.; Moradi, S.; Mahdavi, M. Copper Catalyst-Supported Modified Magnetic Chitosan for the Synthesis of Novel 2-Arylthio-2,3-dihydroquinazolin-4(1H)-one Derivatives via Chan–Lam Coupling. Inorganics 2022, 10, 231. [Google Scholar] [CrossRef]
  47. Wu, F.; Ma, M.; Xie, J. Additive Effects on Copper-Catalyzed Tandem Reactions. Asian J. Org. Chem. 2019, 8, 755–766. [Google Scholar] [CrossRef]
  48. Fihri, A.; Cha, D.; Bouhrara, M.; Almana, N.; Polshettiwar, V. Fibrous Nano-Silica (KCC-1)-Supported Palladium Catalyst: Suzuki Coupling Reactions Under Sustainable Conditions. ChemSusChem 2012, 5, 85–89. [Google Scholar] [CrossRef]
  49. Miao, T.; Wang, L. Regioselective synthesis of 1, 2, 3-triazoles by use of a silica-supported copper (I) catalyst. Synthesis 2008, 2008, 363–368. [Google Scholar] [CrossRef]
  50. Chassaing, S.; Sido, A.S.; Alix, A.; Kumarraja, M.; Pale, P.; Sommer, J. “Click Chemistry” in Zeolites: Copper (I) Zeolites as New Heterogeneous and Ligand-Free Catalysts for the Huisgen [3 + 2] Cycloaddition. Chem. Eur. J. 2008, 14, 6713–6721. [Google Scholar] [CrossRef]
  51. Lipshutz, B.H.; Taft, B.R. Heterogeneous Copper-in-Charcoal-Catalyzed Click Chemistry. Angew. Chem. Int. Ed. 2006, 45, 8235–8238. [Google Scholar] [CrossRef] [PubMed]
  52. Girard, C.; Onen, E.; Aufort, M.; Beauviere, S.; Samson, E.; Herscovici, J. Reusable polymer-supported catalyst for the [3 + 2] Huisgen cycloaddition in automation protocols. Org. Lett. 2006, 8, 1689–1692. [Google Scholar] [CrossRef] [PubMed]
  53. Liu, G.; Lu, X. Cationic Palladium Complex Catalyzed Highly Enantioselective Intramolecular Addition of Arylboronic Acids to Ketones. A Convenient Synthesis of Optically Active Cycloalkanols. J. Am. Chem. Soc. 2006, 128, 16504–16505. [Google Scholar] [CrossRef] [PubMed]
  54. Bosica, G.; Zammit, R. One-pot multicomponent nitro-Mannich reaction using a heterogeneous catalyst under solvent-free conditions. PeerJ 2018, 6, e5065. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  55. Sirion, U.; Bae, Y.J.; Lee, B.S.; Chi, D.Y. Ionic Polymer Supported Copper(I): A Reusable Catalyst for Huisgen’s 1,3-Dipolar Cycloaddition. Synlett 2008, 2008, 2326–2330. [Google Scholar] [CrossRef]
  56. Chavan, P.V.; Pandit, K.S.; Desai, U.V.; Kulkarni, M.A.; Wadgaonkar, P.P. Cellulose supported cuprous iodide nanoparticles (Cell-CuI NPs): A new heterogeneous and recyclable catalyst for the one pot synthesis of 1,4-disubstituted–1,2,3-triazoles in water. RSC Adv. 2014, 4, 42137–42146. [Google Scholar] [CrossRef]
  57. Subudhi, S.; Rath, D.; Parida, K. A mechanistic approach towards the photocatalytic organic transformations over functionalised metal organic frameworks: A review. Catal. Sci. Technol. 2018, 8, 679–696. [Google Scholar] [CrossRef]
  58. Wang, Z.; Zhou, X.; Gong, S.; Xie, J. MOF-Derived Cu@N-C Catalyst for 1,3-Dipolar Cycloaddition Reaction. Nanomaterials 2022, 12, 1070. [Google Scholar] [CrossRef]
  59. Mollabagher, H.; Taheri, S.; Mojtahedi, M.; Seyedmousavi, S.A. Cu-metal organic frameworks (Cu-MOF) as an environment-friendly and economical catalyst for one pot synthesis of tacrine derivatives. RSC Adv. 2020, 10, 1995–2003. [Google Scholar] [CrossRef] [Green Version]
  60. Ullah, S.; Akram, B.; Ali, H.; Zhang, H.; Yang, H.; Liu, Q.; Wang, X. 2-Methylimidazole assisted ultrafast synthesis of carboxylate-based metal–organic framework nano-structures in aqueous medium at room temperature. Sci. Bull. 2019, 64, 1103–1109. [Google Scholar] [CrossRef]
  61. Koczkur, K.M.; Mourdikoudis, S.; Polavarapu, L.; Skrabalak, S.E. Polyvinylpyrrolidone (PVP) in nanoparticle synthesis. Dalton Trans. 2015, 44, 17883–17905. [Google Scholar] [CrossRef] [Green Version]
  62. Gniewek, A.; Trzeciak, A.M.; Ziółkowski, J.J.; Kępiński, L.; Wrzyszcz, J.; Tylus, W. Pd-PVP colloid as catalyst for Heck and carbonylation reactions: TEM and XPS studies. J. Catal. 2005, 229, 332–343. [Google Scholar] [CrossRef]
  63. Joshi, N.; Banerjee, S. PVP coated copper–iron oxide nanocomposite as an efficient catalyst for Click reactions. Tetrahedron Lett. 2015, 56, 4163–4169. [Google Scholar] [CrossRef]
  64. Raut, D.; Wankhede, K.; Vaidya, V.; Bhilare, S.; Darwatkar, N.; Deorukhkar, A.; Trivedi, G.; Salunkhe, M. Copper nanoparticles in ionic liquids: Recyclable and efficient catalytic system for 1,3-dipolar cycloaddition reaction. Catal. Commun. 2009, 10, 1240–1243. [Google Scholar] [CrossRef]
  65. Zhang, Z.; Dong, C.; Yang, C.; Hu, D.; Long, J.; Wang, L.; Li, H.; Chen, Y.; Kongthe, D. Stabilized Copper(I) Oxide Nanoparticles Catalyze Azide-Alkyne Click Reactions in Water. Adv. Synth. Catal. 2010, 352, 1600–1604. [Google Scholar] [CrossRef]
  66. Koszelewski, D.; Ostaszewski, R. Biocatalytic Promiscuity of Lipases in Carbon-Phosphorus Bond Formation. ChemCatChem 2019, 11, 2554–2558. [Google Scholar] [CrossRef]
  67. Koszelewski, D.; Ostaszewski, R.; Smigielski, P.; Hrunyk, A.; Kramkowski, K.; Laskowski, Ł.; Laskowska, M.; Lizut, R.; Szymczak, M.; Michalski, J.; et al. Pyridine Derivatives—A New Class of Compounds That Are Toxic to E. coli K12, R2–R4 Strains. Materials 2021, 14, 5401. [Google Scholar] [CrossRef] [PubMed]
  68. Koszelewski, D.; Kowalczyk, P.; Smigielski, P.; Samsonowicz-Górski, J.; Kramkowski, K.; Wypych, A.; Szymczak, M.; Ostaszewski, R. Relationship between Structure and Antibacterial Activity of α-Aminophosphonate Derivatives Obtained via Lipase-Catalyzed Kabachnik-Fields Reaction. Materials 2022, 15, 3846. [Google Scholar] [CrossRef]
  69. Kowalczyk, P.; Wilk, M.; Parul, P.; Szymczak, M.; Kramkowski, K.; Raj, S.; Skiba, G.; Sulejczak, D.; Kleczkowska, P.; Ostaszewski, R. The Synthesis and Evaluation of Aminocoumarin Peptidomimetics as Cytotoxic Agents on Model Bacterial E. coli Strains. Materials 2021, 14, 5725. [Google Scholar] [CrossRef] [PubMed]
  70. Samsonowicz-Górski, J.; Kowalczyk, P.; Koszelewski, D.; Brodzka, A.; Szymczak, M.; Kramkowski, K.; Ostaszewski, R. The Synthesis and Evaluation of Amidoximes as Cytotoxic Agents on Model Bacterial E. coli Strains. Materials 2021, 14, 7577. [Google Scholar] [CrossRef]
  71. Kowalczyk, P.; Trzepizur, D.; Szymczak, M.; Skiba, G.; Kramkowski, K.; Ostaszewski, R. 1,2-Diarylethanols—A New Class of Compounds that Are Toxic to E. coli K12, R2–R4 Strains. Materials 2021, 14, 1025. [Google Scholar] [CrossRef]
  72. Kowalczyk, P.; Madej, A.; Szymczak, M.; Ostaszewski, R. α-Amidoamids as New Replacements of Antibiotics—Research on the Chosen K12, R2–R4 E. coli Strains. Materials 2020, 13, 5169. [Google Scholar] [CrossRef] [PubMed]
  73. Kowalczyk, P.; Gawdzik, B.; Trzepizur, D.; Szymczak, M.; Skiba, G.; Raj, S.; Kramkowski, K.; Lizut, R.; Ostaszewski, R. δ-Lactones—A New Class of Compounds that Are Toxic to E. coli K12 and R2–R4 Strains. Materials 2021, 14, 2956. [Google Scholar] [CrossRef] [PubMed]
  74. Gawdzik, B.; Kowalczyk, P.; Koszelewski, D.; Brodzka, A.; Masternak, J.; Kramkowski, K.; Wypych, A.; Ostaszewski, R. The Evaluation of DHPMs as Biotoxic Agents on Pathogen Bacterial Membranes. Membranes 2022, 12, 238. [Google Scholar] [CrossRef] [PubMed]
  75. Sahrawat, P.; Kowalczyk, P.; Koszelewski, D.; Szymczak, M.; Kramkowski, K.; Wypych, A.; Ostaszewski, R. Influence of Open Chain and Cyclic Structure of Peptidomimetics on Antibacterial Activity in E. coli Strains. Molecules 2022, 27, 3633. [Google Scholar] [CrossRef] [PubMed]
  76. Kowalczyk, P.; Koszelewski, D.; Gawdzik, B.; Samsonowicz-Górski, J.; Kramkowski, K.; Wypych, A.; Lizut, R.; Ostaszewski, R. Promiscuous Lipase-Catalyzed Markovnikov Addition of H-Phosphites to Vinyl Esters for the Synthesis of Cytotoxic α-Acyloxy Phosphonate Derivatives. Materials 2022, 15, 1975. [Google Scholar] [CrossRef]
  77. Kowalczyk, P.; Borkowski, A.; Czerwonka, G.; Cłapa, T.; Cieśla, J.; Misiewicz, A.; Borowiec, M.; Szala, M. The microbial toxicity of quaternary ammonium ionic liquids is dependent on the type of lipopolysaccharide. J. Mol. Liq. 2018, 266, 540–547. [Google Scholar] [CrossRef]
  78. Borkowski, A.; Kowalczyk, P.; Czerwonka, G.; Ciésla, J.; Cłapa, T.; Misiewicz, A.; Szala, M.; Drabik, M. Interaction of quaternary ammonium ionic liquids with bacterial membranes—Studies with Escherichia coli R1–R4-type lipopolysaccharides. J. Mol. Liq. 2017, 246, 282–289. [Google Scholar] [CrossRef]
  79. Maciejewska, A.; Kaszowska, M.; Jachymek, W.; Lugowski, C.; Lukasiewicz, J. Lipopolysaccharide-linked Enterobacterial Common Antigen (ECALPS) Occurs in Rough Strains of Escherichia coli R1, R2, and R4. Int. J. Mol. Sci. 2020, 21, 6038. [Google Scholar] [CrossRef]
  80. Prost, M.E.; Prost, R. Basic parameters of evaluation of the effectiveness of antibiotic therapy. Ophtha Ther. 2017, 4, 233–236. [Google Scholar] [CrossRef]
  81. Ramnial, T.; Taylor, S.A.; Clyburne, J.A.C.; Walsby, C.J. Grignard reagents in ionic solvents: Electron transfer reactions and evidence for facile Br–Mg exchange. Chem. Commun. 2007, 20, 2066–2068. [Google Scholar] [CrossRef] [PubMed]
  82. Wu, J.; Zhang, J.; Soto-Acosta, R.; Mao, L.; Lian, J.; Chen, K.; Pillon, G.; Zhang, G.; Geraghty, R.J.; Zheng, S. One-Pot Synthesis of 1-Hydroxyacridones from para-Quinols and ortho-Methoxycarbonylaryl Isocyanates. J. Org. Chem. 2020, 85, 4515–4524. [Google Scholar] [CrossRef] [PubMed]
  83. Novak, M.; Poturalski, M.J.; Johnson, W.L.; Jones, M.P.; Wang, Y.; Glover, S.A. 4‘-Substituted-4-biphenylyloxenium Ions:  Reactivity and Selectivity in Aqueous Solution. J. Org. Chem. 2006, 71, 3778–3785. [Google Scholar] [CrossRef] [PubMed]
  84. Tang, T.; Harned, A.M. Experimental evidence for the formation of cationic intermediates during iodine(III)-mediated oxidative dearomatization of phenols. Org. Biomol. Chem. 2018, 16, 6871–6874. [Google Scholar] [CrossRef]
  85. Li, P.; Sisto, T.J.; Darzi, E.R.; Jasti, R. The Effects of Cyclic Conjugation and Bending on the Optoelectronic Properties of Paraphenylenes. Org. Lett. 2014, 16, 182–185. [Google Scholar] [CrossRef] [PubMed]
  86. Yakura, T.; Omoto, M.; Yamauchi, Y.; Tian, Y.; Ozono, A. Hypervalent iodine oxidation of phenol derivatives using a catalytic amount of 4-iodophenoxyacetic acid and Oxone® as a co-oxidant. Tetrahedron 2010, 66, 5833–5840. [Google Scholar] [CrossRef]
  87. Yang, B.; Yao, W.; Xia, X.-F.; Wang, D. Mn-Catalyzed 1,6-conjugate addition/aromatization of para-quinone methides. Org. Biomol. Chem. 2018, 16, 4547–4557. [Google Scholar] [CrossRef]
  88. Zhang, S.; Song, F.; Zhao, D.; You, J. Tandem oxidation–oxidative C–H/C–H cross-coupling: Synthesis of arylquinones from hydroquinones. Chem. Commun. 2013, 49, 4558–4560. [Google Scholar] [CrossRef]
Ijms 24 01623 sch001 550
Scheme 1. Copper catalyzed 1,2-addition of boronic acid derivatives to 1,4-benzoquinones.
Scheme 1. Copper catalyzed 1,2-addition of boronic acid derivatives to 1,4-benzoquinones.
Ijms 24 01623 sch001
Ijms 24 01623 g001 550
Figure 1. Biologically active 4-substituted 4-hydroxycyclohexa-2,5-dienones class (p-quinols).
Figure 1. Biologically active 4-substituted 4-hydroxycyclohexa-2,5-dienones class (p-quinols).
Ijms 24 01623 g001
Ijms 24 01623 g002 550
Figure 2. Dynamic light scattering (DLS) measurements for hydrodynamic diameters of colloidal copper particles.
Figure 2. Dynamic light scattering (DLS) measurements for hydrodynamic diameters of colloidal copper particles.
Ijms 24 01623 g002
Ijms 24 01623 g003 550
Figure 3. Reusability of CuI-PVP catalytic system in 1 synthesis. Phenylboronic acid (1 mmol), benzoquinone (1 mmol), CuI (0.1 mmol, 10 mol%), and PVP (10 mol%) in distilled water (4 mL) for 8 h, magnetic stirring 600 rpm, reaction shielded from light with aluminum foil.
Figure 3. Reusability of CuI-PVP catalytic system in 1 synthesis. Phenylboronic acid (1 mmol), benzoquinone (1 mmol), CuI (0.1 mmol, 10 mol%), and PVP (10 mol%) in distilled water (4 mL) for 8 h, magnetic stirring 600 rpm, reaction shielded from light with aluminum foil.
Ijms 24 01623 g003
Ijms 24 01623 g004 550
Figure 4. Synthesis of various p-quinols under optimized conditions. Reaction conditions: arylboronic acid (1 mmol), benzoquinone (1 mmol), CuI (0.1 mmol, 10 mol%), and PVP (10 mol%) in distilled water (4 mL) for 8 h, magnetic stirring 600 rpm, reaction shielded from light with aluminum foil. Yields in brackets provided for isolated products 1–10.
Figure 4. Synthesis of various p-quinols under optimized conditions. Reaction conditions: arylboronic acid (1 mmol), benzoquinone (1 mmol), CuI (0.1 mmol, 10 mol%), and PVP (10 mol%) in distilled water (4 mL) for 8 h, magnetic stirring 600 rpm, reaction shielded from light with aluminum foil. Yields in brackets provided for isolated products 1–10.
Ijms 24 01623 g004
Ijms 24 01623 g005 550
Figure 5. Parent benzo- and hydroquinones 11–14.
Figure 5. Parent benzo- and hydroquinones 11–14.
Ijms 24 01623 g005
Ijms 24 01623 g006 550
Figure 6. Minimum inhibitory concentration (MIC) of the p-quinols 1-10 and parent benzo- and hydroquinones 11–14 in model bacterial strains. The x-axis features compounds 1–14 used sequentially. The y-axis shows the MIC value in µg/mL−1.
Figure 6. Minimum inhibitory concentration (MIC) of the p-quinols 1-10 and parent benzo- and hydroquinones 11–14 in model bacterial strains. The x-axis features compounds 1–14 used sequentially. The y-axis shows the MIC value in µg/mL−1.
Ijms 24 01623 g006
Ijms 24 01623 g007 550
Figure 7. Minimum bactericidal concentration (MBC) of the p-quinols. The x-axis features compounds 1–14 used sequentially. The y-axis shows the MIC value in µg/mL−1.
Figure 7. Minimum bactericidal concentration (MBC) of the p-quinols. The x-axis features compounds 1–14 used sequentially. The y-axis shows the MIC value in µg/mL−1.
Ijms 24 01623 g007
Ijms 24 01623 g008 550
Figure 8. The ratio of MBC/MIC of the p-quinols. The x-axis features compounds 1–14 used sequentially. The y-axis shows the MIC value in µg/mL−1.
Figure 8. The ratio of MBC/MIC of the p-quinols. The x-axis features compounds 1–14 used sequentially. The y-axis shows the MIC value in µg/mL−1.
Ijms 24 01623 g008
Ijms 24 01623 g009 550
Figure 9. Percentage of plasmid DNA recognized by Fpg enzyme (y-axis) with model bacterial, K12, and R2–R4 strains (x-axis).
Figure 9. Percentage of plasmid DNA recognized by Fpg enzyme (y-axis) with model bacterial, K12, and R2–R4 strains (x-axis).
Ijms 24 01623 g009
Ijms 24 01623 g010 550
Figure 10. Examples of MIC with model bacterial strains K12, R2, R3, and R4 for studying antibiotics ciprofloxacin (cipro), bleomycin (bleo), and cloxacillin (clox). The x-axis features antibiotics used sequentially. The y-axis features the MIC value in µg/mL−1.
Figure 10. Examples of MIC with model bacterial strains K12, R2, R3, and R4 for studying antibiotics ciprofloxacin (cipro), bleomycin (bleo), and cloxacillin (clox). The x-axis features antibiotics used sequentially. The y-axis features the MIC value in µg/mL−1.
Ijms 24 01623 g010
Ijms 24 01623 g011 550
Figure 11. Percentage of bacterial DNA recognized by Fpg enzyme in model bacterial strains after ciprofloxacin, bleomycin, and cloxacillin treatment. The compounds were statistically significant at p < 0.05 (Supplementary Materials Figure S3).
Figure 11. Percentage of bacterial DNA recognized by Fpg enzyme in model bacterial strains after ciprofloxacin, bleomycin, and cloxacillin treatment. The compounds were statistically significant at p < 0.05 (Supplementary Materials Figure S3).
Ijms 24 01623 g011
Table
Table 1. Model copper catalyzed 1,2-addition of phenylboronic acid to 1,4-benzoquinone. a Optimization studies.
Table 1. Model copper catalyzed 1,2-addition of phenylboronic acid to 1,4-benzoquinone. a Optimization studies.
Ijms 24 01623 i001
EntryAdditiveT (°C)SolventYield 1 [%] dYield 15 [%] d
1None20H2O519
2Amberlite IRA-40020H2O587
3Montmorillonite20H2O64<1
4Amberlyst20H2O18<1
5Dowex-120H2O686
6Silica gel20H2O508
7Al2O320H2O5411
8Cellulose20H2O49<1
9MOF-120H2O3811
10MOF-220H2O42<1
11PVP 8000 20H2O74<1
12PVP 350020H2O84<1
13PVP 2400020H2O62<1
14PVP 3500 [b]20H2O81<1
15PVP 3500 [c]20H2O79<1
16PVP 3500 30H2O89<1
17PVP 350040H2O83<1
18PVP 350030Methanol71<1
a Reaction conditions: phenylboronic acid (1 mmol), benzoquinone (1 mmol), CuI (0.1 mmol, 10 mol%), and additive (10 mol%) in distilled water (4 mL) for 8 h, magnetic stirring 600 rpm, reaction shielded from light with aluminum foil. b PVP (15 mol%), c PVP (20 mol%). d Yield of the isolated product after chromatography on silica gel.
Table
Table 2. Statistical analysis of all analyzed compounds by MIC, MBC, and MBC/MIC; <0.05 *, <0.01 **, <0.001 ***.
Table 2. Statistical analysis of all analyzed compounds by MIC, MBC, and MBC/MIC; <0.05 *, <0.01 **, <0.001 ***.
No. of Samples5710, 11Type of Test
K12******MIC
R2******MIC
R3******MIC
R4******MIC
K12*******MBC
R2*******MBC
R3*******MBC
R4*******MBC
K12*******MBC/MIC
R2*******MBC/MIC
R3*******MBC/MIC
R4*******MBC/MIC
Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content.

Share and Cite

MDPI and ACS Style

Koszelewski, D.; Kowalczyk, P.; Samsonowicz-Górski, J.; Hrunyk, A.; Brodzka, A.; Łęcka, J.; Kramkowski, K.; Ostaszewski, R. Synthesis and Antimicrobial Activity of the Pathogenic E. coli Strains of p-Quinols: Additive Effects of Copper-Catalyzed Addition of Aryl Boronic Acid to Benzoquinones. Int. J. Mol. Sci. 2023, 24, 1623. https://doi.org/10.3390/ijms24021623

AMA Style

Koszelewski D, Kowalczyk P, Samsonowicz-Górski J, Hrunyk A, Brodzka A, Łęcka J, Kramkowski K, Ostaszewski R. Synthesis and Antimicrobial Activity of the Pathogenic E. coli Strains of p-Quinols: Additive Effects of Copper-Catalyzed Addition of Aryl Boronic Acid to Benzoquinones. International Journal of Molecular Sciences. 2023; 24(2):1623. https://doi.org/10.3390/ijms24021623

Chicago/Turabian Style

Koszelewski, Dominik, Paweł Kowalczyk, Jan Samsonowicz-Górski, Anastasiia Hrunyk, Anna Brodzka, Justyna Łęcka, Karol Kramkowski, and Ryszard Ostaszewski. 2023. "Synthesis and Antimicrobial Activity of the Pathogenic E. coli Strains of p-Quinols: Additive Effects of Copper-Catalyzed Addition of Aryl Boronic Acid to Benzoquinones" International Journal of Molecular Sciences 24, no. 2: 1623. https://doi.org/10.3390/ijms24021623

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop