
==== Front
J Org Chem
J Org Chem
jo
joceah
The Journal of Organic Chemistry
0022-3263
1520-6904
American Chemical Society

39233358
10.1021/acs.joc.4c00997
Article
Telluride-Based Pillar[5]arene: A Recyclable Catalyst for Alkylation Reactions in Aqueous Solution
Nobre Patrick C. †
Cordeiro Pâmella †
Chipoline Ingrid C. †
Menezes Victor †
Santos Kaila V. S. †
Ángel Alix Y. Bastidas ‡
Alberto Eduardo E. *‡
https://orcid.org/0000-0001-9413-7638
Nascimento Vanessa *†
† SupraSelen Laboratory, Department of Organic Chemistry, Universidade Federal Fluminense, Campus do Valonguinho, Niterói, Rio de Janeiro 24020-141, Brazil
‡ Departamento de Química, Universidade Federal de Minas Gerais−UFMG, Belo Horizonte, Minas Gerais 31270-901, Brazil
* Email: albertoee.ufmg@gmail.com.
* Email: nascimentovanessa@id.uff.br.
05 09 2024
20 09 2024
89 18 1298212988
24 04 2024
23 08 2024
10 08 2024
© 2024 The Authors. Published by American Chemical Society
2024
The Authors
https://creativecommons.org/licenses/by/4.0/ Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).

The syntheses of previously unknown sulfide- and telluride-pillar[n]arenes are reported here. These macrocycles, among others, were tested as catalysts for alkylation reactions in aqueous solutions. Telluride-pillar[5]arene (P[5]-TePh) showed the best performance, emulating the behavior of the methyltransferase enzyme cofactor S-adenosyl-l-methionine. Using 1.0 mol % of P[5]-TePh, benzyl bromides reacted with NaCN/NaN3 in water, yielding organic nitriles/azides. The catalyst was recycled and efficiently reused for up to six cycles. 1H NMR experiments indicate a possible interaction between the substrate and P[5]-TePh’s cavity.

CoordenaÃ§Ã£o de AperfeiÃ§oamento de Pessoal de NÃ­vel Superior 10.13039/501100002322 NA FundaÃ§Ã£o de Amparo Ã  Pesquisa do Estado de Minas Gerais 10.13039/501100004901 BPD-00482-22 FundaÃ§Ã£o de Amparo Ã  Pesquisa do Estado de Minas Gerais 10.13039/501100004901 APQ-00349-22 FundaÃ§Ã£o Carlos Chagas Filho de Amparo Ã  Pesquisa do Estado do Rio de Janeiro 10.13039/501100004586 E-26/210.325/2022 FundaÃ§Ã£o Carlos Chagas Filho de Amparo Ã  Pesquisa do Estado do Rio de Janeiro 10.13039/501100004586 E-26/202.911/2019 FundaÃ§Ã£o Carlos Chagas Filho de Amparo Ã  Pesquisa do Estado do Rio de Janeiro 10.13039/501100004586 E-26/200.235/2023 Conselho Nacional de Desenvolvimento CientÃ­fico e TecnolÃ³gico 10.13039/501100003593 CNPq (VN. 310656/2021-4) document-id-old-9jo4c00997
document-id-new-14jo4c00997
ccc-price
==== Body
pmcIntroduction

Enzymes are great catalysts with impressive efficiency, specificity, and selectivity.1,2 Methyltransferases, for instance, promote the transference of a methyl group to a variety of substrates (e.g., proteins, lipids, RNA, and DNA) in biological processes related to metabolism, biosynthesis, and detoxification of exogenous compounds.3−5 The cofactor of this enzyme is a sulfonium salt named S-adenosyl-l-methionine (SAM) 1, which is the donor of the methyl group to a given nucleophile (Figure 1a).6−9 Inspired by the transformation mediated by methyltransferases, many reports in the literature have been disclosed with a focus on the preparation and utilization of SAM and derivatives (including its selenium analog) and their application as group transfer agents in a broader sense.10−15 Structurally simpler SAM derivatives 2, most as sulfonium or selenonium salts,16−22 but rarely telluronium salts,23,24 have also been applied as alkylating agents (Figure 1b).

Figure 1 (a) S-adenosyl-L-methionine (SAM) 1, an electrophile for methylation of nucleophiles; (b) chalcogenonium salts 2 as alkylating agents; (c) representation of a pillar[n]arene.

Synthetic macrocycles with tailored cavities can produce noncovalent bonding interactions with different substrates, resulting in the stabilization and organization of intermediates, offering a different environment for chemical reactions.25 Pillar[n]arenes have emerged as a new generation of supramolecular macrocyclic hosts in the past decade (Figure 1c).26,27 These macrocycles can form inclusion complexes with different small molecules through dipole–dipole interactions, hydrogen bonding, π–π stacking, etc.15,28−46 They have shown several promising applications for drug delivery,31−34 as nanomaterials,35−37 sensors,38−40 and as transmembrane channels.41−43 In organic synthesis, the use of pillar[n]arenes is still little explored, especially owing to their application as catalysts.44−46 Xiao and co-workers reported the synthesis of pillar[5]arenes which when combined with PdCl2(CH3CN)2, could efficiently catalyze Heck coupling reactions of styrene and aryl halides.44 In 2019, Lan and co-workers described a cross-linked porous polymeric material based on pillar[5]quinone, which was used to load Pd-catalyst and prepare a heterogeneous catalyst. The catalyst was highly efficient for Suzuki-coupling reactions and could be recycled and reused six times without any drop in reaction yield.45 Recently, a pillar[5]arene-based [2]rotaxane was designed and developed by Guo and co-workers, which, upon coordination with Pd ions, was efficiently used to catalyze Suzuki couplings.46 Although less reported, there are examples of pillararenes catalyzing reactions in aqueous environments, demonstrating their significant potential as catalysts.47,48

Accordingly, as part of our interest in developing new organochalcogen compounds with privileged molecular structures for different applications,49−53 allied to the synthesis and application of pillar[n]arenes,54−57 we report herein the synthesis of chalcogen-based pillar[5]arenes, including unknown sulfide- and telluride-based pillar[n]arenes. Additionally, we screened their catalytic activity in promoting the alkylation of nucleophiles dissolved in aqueous solutions and the possibility of recycling and reusing them.

Results and Discussion

The monomeric catalysts (M-YPh, where Y = S, Se, or Te) depicted in Table 1 employed in this study were prepared from the corresponding monomeric bromides (M-Br).54 Likewise, the pillar[n]arene catalysts (P[n]-YPh, where n is 5 or 6 and Y = S, Se, or Te) were obtained from the bromide starting material. To date, only the selenium-pillar[n]arene analog is known.58 All catalysts were obtained in good yields (see the Supporting Information for the experimental details). To test their ability to promote an alkylation reaction in aqueous solution, we chose the conversion of benzyl bromide 3a to the corresponding cyanide 4a as the model experiment (Table 1).59−61 Without a catalyst, the reaction of 3a and 2 equiv of NaCN produced only 15% of product 4a after stirring the reaction at room temperature for 24 h as previously reported (entry 1).16 Addition of 5.0 mol % of monomeric catalysts accelerated product formation, especially for the tellurium analog M-TePh. In that case, 45% of benzyl nitrile 4a was obtained after 24 h (entry 4). Next, chalcogen-based pillar[n]arenes were screened. At this time, however, 1.0 mol % of the catalyst was used to keep the same amount of chalcogen in the reaction media (entries 5–10). As observed for the monomeric species, the reaction showed a clear trend between the nature of the chalcogen and the yield observed for product 4a. Telluride P[5]-TePh outperformed all other catalysts, delivering the product in near quantitative yield after 24 h of reaction (Entry 7). We performed experiments with shorter duration and observed that after 12 h the reaction was essentially done (entries 8 and 9). It is noteworthy that the contribution of the pillar[n]arene scaffold to the reaction outcome. Keeping the catalytic amount of chalcogen the same in all experiments, 4a formation was significantly increased using P[5]-TePh compared to the reaction using M-TePh (entries 4 and 7). Moreover, it was observed that the pillar[n]arene cavity size was not critical for the catalytic activity under identical reaction conditions. P[6]-TePh performed similarly to P[5]-TePh (entries 7 and 10). Therefore, we continued our study with P[5]-TePh due to its easier preparation when compared to P[6]-TePh.

Table 1 Optimization of the Reaction Conditionsa

entry	catalyst	mol %	yield (%)b	
1	none	0.0	15	
2	M-SPh	5.0	5	
3	M-SePh	5.0	29	
4	M-TePh	5.0	45	
5	P[5]-SPh	1.0	22	
6	P[5]-SePh	1.0	55	
7	P[5]-TePh	1.0	96	
8c	P[5]-TePh	1.0	92	
9d	P[5]-TePh	1.0	40	
10	P[6]-TePh	1.0	85	
a Reaction conditions: benzyl bromide (0.174 mmol), catalyst (0.0–5.0 mol %), NaCN (0.348 mmol) in H2O (1.0 mL) at 25 °C for 24 h.

b Isolated yield.

c 12 h of reaction.

d 6 h of reaction.

Next, we applied the best reaction conditions to convert other substrates to nitriles catalyzed by 1.0 mol % of P[5]-TePh in aqueous solution (Figure 2). First, we observed that the yield of the conversion of benzyl bromide to 3a was not affected on a larger scale. Then, aryl bromides assembled with electron-donating or electron-withdrawing groups were converted to the corresponding nitriles 4b–h in reasonable to good yields. Noteworthy, no clear correlation between the electronic properties and product yield was observed for these substrates. Product 4i obtained in 40% yield revealed that α-carbonyl bromides are feasible substrates for this transformation. Additionally, nitrile 4n was prepared in 68% yield when the same reaction conditions were applied using cinnamyl chloride as the substrate. On the contrary, products 4j-m from an electron-rich benzyl bromide, allyl bromide, or alkyl bromides could not be produced in desirable amounts. To improve the yield of product 4j, we prepared the bromide starting material and immediately used it in the reaction. However, the strong electron donation capacity of the dimethylamino substituent triggered its decomposition faster than the reaction with the nucleophile. The results collectively indicate that at the current stage, regardless of the substrate solubility in water, only activated starting materials toward displacement reactions are feasible substrates for the transformation. The reaction conditions for effective conversions of less reactive aliphatic halides or to obtain products with lower boiling points should be better designed. Finding better catalysts is crucial in this context.

Figure 2 Substrate scope for conversion of halides to cyanides catalyzed by P[5]-TePh. aIsolated yield. bCinnamyl chloride was used as substrate.

To demonstrate the effectiveness of this protocol, we studied the conversion of selected substrates to azides using NaN3 as the nucleophile (Figure 3). Gratifyingly, benzyl bromide was converted to respective azide 5a in 90% yield. Importantly, without P[5]-TePh, only 8% 5a was obtained. Other benzyl bromides containing electron-donating or electron-withdrawing groups, an α-carbonyl derivative, and cinnamyl chloride were used as substrates. Products 5b-5g were obtained in reasonable to good yields, mirroring the results obtained with cyanide as the nucleophilic species.

Figure 3 Substrate scope for conversion of halides to azides catalyzed by P[5]-TePh. aIsolated yield. bCinnamyl chloride was used as substrate.

Due to their electron-rich cavities, pillar[n]arenes have excellent host–guest properties, forming stable complexes through charge transfer interactions (e.g., cation-π interactions, CH-π interactions, and π–π stacking).31−34 To further understand the interactions between substrates and P[5]-TePh in the reaction, we performed 1H NMR analysis of a mixture of P[5]-TePh and bromide 3i, chosen because it has a higher molecular weight (more experimental details and 1H NMR spectra are given in the Supporting Information). Although small, various signal shifts could be observed for catalyst and bromide 3i (Figure 4a). These results might suggest the formation of an inclusion complex between the pillar[n]arene and the substrate. In addition, since signal shifts were observed for the aromatic protons of 3i, we suggest that the aryl group of 3i could be engulfed into the P[5]-TePh cavity, while the CH2 group was not. These observations are consistent with previous reports, considering that the cavity size of the pillar[5]arenes can accommodate a benzene ring62 and lead to the formation of an efficient host–guest complex.63−69

Figure 4 (a) Signal shifts observed by 1H NMR of a mixture P[5]-TePh and 3i in CDCl3; (b) structure of the proposed active alkylating agent.

Nevertheless, the catalytic activity of pillar[n]arene catalysts P[n]-YPh as an alkylating agent is not solely related to the size of the cavity or its host–guest interactions with the substrate. The chalcogen atom is crucial in the substrate conversion to products. Based on our previous results and reported literature,70−73 we propose that the active species is a telluronium salt, as depicted in Figure 4b.

Finally, developing safer and greener organic reactions is a major goal nowadays.74,75 Accordingly, in addition to water being used as the reaction solvent, we studied the possibility of recovering and reusing catalyst P[5]-TePh. To our delight, we found that after the extraction of the reaction mixture, benzyl bromide and product 4a could be separated from P[5]-TePh by washing the crude mixture with hexanes. In this way, the catalyst could be reused for another reaction after water and NaCN addition. This process could be efficiently repeated during 5 cycles with excellent catalyst recovery and without reducing the reaction yield on 4a formation. Although the reaction yield remained constant, after the fifth cycle, a drop in the recovery of the catalyst was observed (Figure 5).

Figure 5 Evaluation of recovery and reuse of P[5]-TePh on conversion of BnBr to 4a.

Conclusions

In conclusion, we have described, for the first time, the synthesis of sulfur- and tellurium-based pillar[n]arenes. These novel macrocycles were obtained in excellent yields via a simple nucleophilic substitution reaction from the corresponding bromide. The ability of monomeric catalysts M-YPh (5.0 mol %) and pillar[n]arene catalysts P[n]-YPh (1.0 mol %) to promote the conversion of bromides to the related nitriles or azide in an aqueous solution containing NaCN or NaN3 was investigated. It was found that the chalcogen nature and the pillar cavity size are critical for catalytic performance. 1H NMR experiments of mixtures of P[5]-TePh and a substrate indicated possible host–guest interactions in the form of an inclusion complex. Moreover, it was feasible to perform the reaction on a larger scale, and the catalyst P[5]-TePh could be recovered and reused effectively for five reaction cycles. Inspired by these results, we are pursuing further developments, including the design of new chalcogen-pillar[n]arenes and their application to a broader panel of organic transformations.

Experimental Section

General Remarks

The reactions were monitored by TLC carried out on Merck silica gel (60 F254) using UV light as a visualizing agent, an iodine chamber, and 5% vanillin in 10% H2SO4 and heat as developing agents. Baker silica gel (particle size 0.040–0.063 mm) was used for flash chromatography. Proton nuclear magnetic resonance spectra (1H NMR) were obtained on a Varian AS-400 or a Bruker Avance NEO 500 MHz employing a direct broadband probe at 500 MHz. Spectra are recorded in CDCl3 solutions. Chemical shifts are reported in parts per million, referenced to tetramethylsilane (TMS) as the internal reference. Coupling constants (J) are reported in Hertz. Abbreviations to denote the multiplicity of a particular signal are s (singlet), d (doublet), dd (doublet of doublets), ddd (doublet of doublet of doublets), q (quartet), quint (quintet), sex (sextet), t (triplet), and m (multiplet). Carbon-13 (13C{1H} NMR) nuclear magnetic resonance spectra and Carbon-13-attached proton test (13C{1H}-APT NMR) nuclear magnetic resonance spectra were obtained on a Varian AS-400 or on Bruker Avance NEO 500 MHz employing a direct broadband probe at 125 MHz. The high-resolution atmospheric pressure chemical ionization mass spectrometry (APCI-QTOF) and electrospray ionization (ESI-QTOF) mass spectrometry analyses were performed on a Bruker Daltonics micrOTOF-Q II instrument in operating positive mode. The samples were solubilized in HPLC-grade acetonitrile and injected into the source by means of a syringe pump at a flow rate of 5.0 μL min-1. The following instrument parameters were applied: capillary and cone voltages were set to +4000 and −500 V, respectively, with a desolvation temperature of 180 °C. For data acquisition, processing, and isotope simulations, Compass 1.3 for micrOTOF-Q II software (Bruker daltonics, USA) was used. Melting point (mp) values were measured in a Fisatom 430D instrument with a 0.1 °C precision. The Fourier transform infrared (FTIR) measurements were performed on a Nicolet iS50 (Thermo Fisher Scientific). UV–visible absorption spectra were obtained in the UV/visible range (from 200 to 800 nm) using a Varian Cary 50 Scan spectrophotometer and quartz cuvettes with a path length of 10 mm and 1.5 mL. UV–visible spectra were recorded using dichloromethane. Final concentrations of compounds: P[5]Br, P[5]TePh, and P[6]TePh = 1,0 μM. P[6]Br = 0,2 μM.

General Procedure for Alkylation of NaCN Catalyzed by P[5]-TePh

A 10.0 mL round-bottomed glass vial was added with the appropriate alkyl bromide 3a-n (0.174 mmol), P[5]-TePh (0.00174 mmol, 8.0 mg; 1.0 mol %), and water (1.0 mL). The resulting mixture was stirred at room temperature for 5 min. After this, NaCN (0.348 mmol, 17.1 mg) was added, and the mixture was stirred for an additional 12 h. The reactions were monitored by TLC until the total disappearance of the starting materials (the progress of the reaction could also be visually observed. See Figure S1). After that, the reaction mixture was extracted with ethyl acetate (3 × 15.0 mL). The combined organic layers were dried over Na2SO4 and concentrated under a vacuum. The residue was purified by preparative TLC using hexane/ethyl acetate (90:10) as the eluent.

Data Availability Statement

The data underlying this study are available in the published article and its Supporting Information.

Supporting Information Available

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.joc.4c00997.General procedures for compounds M-SPh, M-SePh, M-TePh, P[5]-SPh, P[5]-SePh, P[5]-TePh, P[6]-TePh; general procedure for the synthesis of compounds 4a–n and 5a–g; general procedure for Gram-scale reaction; general procedure for recovery and reuse of the catalyst P[5]-TePh; experiments to detect the interactions between substrates and P[5]-TePh; and spectral data and copies of NMR spectra for all compounds (PDF)

Supplementary Material

jo4c00997_si_001.pdf

Author Contributions

The manuscript was written with all authors’ contributions. All authors have approved the final version of the manuscript.

The Article Processing Charge for the publication of this research was funded by the Coordination for the Improvement of Higher Education Personnel - CAPES (ROR identifier: 00x0ma614).

The authors declare no competing financial interest.

Acknowledgments

This study was financed in part by Conselho Nacional de Desenvolvimento Científico e Tecnológico – CNPq (VN. 310656/2021-4) and Coordenação de Aperfeiçoamento de Pessoal de Nível Superior – CAPES. AYBA and EEA are grateful to Fundação de Amparo à Pesquisa do Estado de Minas Gerais – FAPEMIG for the financial support of this research (grant numbers APQ-00349-22 and BPD-00482-22). VN, PCN, ICC, PC, VHMC, KV thank the Fundação Carlos Chagas Filho de Amparo à Pesquisa no Estado do Rio de Janeiro (E-26/202.911/2019, E-26/210.325/2022, and E-26/200.235/2023) and INCT- Catalysis for the financial support. The authors would like to thank the Laboratório Multiusuário de RMN da UFF – UFFLaReMN, especially to Michael Anderson P. Marques and Lívia Goneli, for the NMR analysis performed.
==== Refs
References

Hedstrom L. Enzyme Specificity and Selectivity. In Encyclopedia of Life Sciences (ELS); John Wiley & Sons, Ltd: Chichester, 2010.
Chen K. ; Arnold F. H. Engineering new catalytic activities in enzymes. Nat. Catal. 2010, 3 (3 ), 203–213. 10.1038/s41929-019-0385-5.
Rudenko A. Y. ; Mariasina S. S. ; Sergiev P. V. ; Polshalov V. I. Analogs of S-Adenosyl-L-Methionine in Studies of Methyltransferases. Mol. Biol. 2022, 56 (2 ), 229–250. 10.1134/S002689332202011X.35440827
Francioso A. ; Fanelli S. ; d’Erme M. ; Lendaro E. ; Miraglia N. ; Fontana M. ; Carvallaro R. A. ; Mosca L. Pharmacokinetic properties of a novel formulation of S-adenosyl-L-methionine phytate. Amino Acids 2021, 53 (10 ), 1559–1568. 10.1007/s00726-021-03076-7.34536129
Struck A. ; Thompson M. L. ; Wong L. S. ; Micklefield J. S-Adenosyl-Methionine-Dependent Methyltransferases: Highly Versatile Enzymes in Biocatalysis, Biosynthesis and Other Biotechnological Applications. ChemBioChem. 2012, 13 (18 ), 2642–2655. 10.1002/cbic.201200556.23180741
Lv Y.-B. ; Chen C. ; Yu Q.-M. ; Lyu L. ; Peng Y.-F. ; Tan X.-D. Synthesis and biological evaluation of novel pentanediamide derivatives as S-adenosyl-L-homocysteine hydrolase inhibitors. Bioorg. Med. Chem. Lett. 2022, 72 (7 ), 128880 10.1016/j.bmcl.2022.128880.35809817
Roje S. S-Adenosyl-L-methionine: Beyond the universal methyl group donor. Phytochemistry 2006, 67 (15 ), 1686–1698. 10.1016/j.phytochem.2006.04.019.16766004
Zhang J. ; Zheng Y. G. SAM/SAH Analogs as Versatile Tools for SAM-Dependent Methyltransferases. ACS Chem. Biol. 2016, 11 (3 ), 583–597. 10.1021/acschembio.5b00812.26540123
Stillson N. J. ; Anderson K. E. ; Reich N. O. In silico study of selective inhibition mechanism of S-adenosyl-L-methionine analogs for human DNA methyltransferase 3A. Comput. Biol. Chem. 2023, 102 (3 ), 107796 10.1016/j.compbiolchem.2022.107796.36495748
Cornelissen N. V. ; Michailidou F. ; Muttach F. ; Rau K. ; Rentmeister A. Nucleoside-modified AdoMet analogues for differential methyltransferase targeting. Chem. Commun. 2020, 56 (14 ), 2115–2118. 10.1039/C9CC07807J.
Hartstock K. ; Nilges B. S. ; Ovcharenko A. ; Cornelissen N. V. ; Püllen N. ; Lawrence-Dörner A. ; Leidel S. A. ; Rentmeister A. Enzymatic or In Vivo Installation of Propargyl Groups in Combination with Click Chemistry for the Enrichment and Detection of Methyltransferase Target Sites in RNA. Angew. Chem., Int. Ed. 2018, 57 (21 ), 6342–6346. 10.1002/anie.201800188.
Muttach F. ; Rentmeister A. A Biocatalytic Cascade for Versatile One-Pot Modification of mRNA Starting from Methionine Analogues. Angew. Chem., Int. Ed. 2016, 55 (5 ), 1917–1920. 10.1002/anie.201507577.
Tang Q. ; Grathwol C. W. ; Aslan-Uzel A. S. ; Wu S. ; Link A. ; Pavlidis I. V. ; Badenhorst C. P. S. ; Bornscheuer U. T. Directed Evolution of a Halide Methyltransferase Enables Biocatalytic Synthesis of Diverse SAM Analogs. Angew. Chem., Int. Ed. 2021, 60 (3 ), 1524–1527. 10.1002/anie.202013871.
Herbert A. J. ; Shepherd S. A. ; Cronin V. A. ; Bennett M. R. ; Sung R. ; Micklefield J. Engineering Orthogonal Methyltransferases to Create Alternative Bioalkylation Pathways. Angew. Chem., Int. Ed. 2020, 59 (35 ), 14950–14956. 10.1002/anie.202004963.
Arora S. ; Horne W. S. ; Islam K. J. Engineering Methyllysine Writers and Readers for Allele-Specific Regulation of Protein-Protein Interactions. Am. Chem. Soc. 2019, 141 (39 ), 15466–15470. 10.1021/jacs.9b05725.
Angel A. ; Campos P. ; Alberto E. E. Synthetic application of chalcogenonium salts: beyond sulfonium. Org. Biomol. Chem. 2023, 21 (2 ), 223–236. 10.1039/d2ob01822e.36503911
Martins N. S. ; Ángel A. Y. B. ; Anghinoni J. M. ; Lenardão E. J. ; Barcellos T. ; Alberto E. E. From Stoichiometric Reagents to Catalytic Partners: Selenonium Salts as Alkylating Agents for Nucleophilic Displacement Reactions in Water. Adv. Synth. Catal. 2022, 364 (1 ), 87–93. 10.1002/adsc.202100797.
Taimoory S. M. ; Cataldo V. A. ; Schäfer A. ; Trant J. F. ; Guterman R. Not-So-Innocent Anions Determine the Mechanism of Cationic Alkylators. Chem.—Eur. J. 2021, 27 (10 ), 3440–3448. 10.1002/chem.202004208.33137244
Berger F. ; Alvarez E. M. ; Frank N. ; Bohdan K. ; Kondratiuk M. ; Torkowski L. ; Engl P. S. ; Barletta J. ; Ritter T. Cine-Substitutions at Five-Membered Hetarenes Enabled by Sulfonium Salts. Org. Lett. 2020, 22 (14 ), 5671–5674. 10.1021/acs.orglett.0c02067.32640160
Guterman R. ; Miao H. ; Antonietti M. J. Thioimidazolium Ionic Liquids as Tunable Alkylating Agents. Org. Chem. 2018, 83 (2 ), 684–689. 10.1021/acs.joc.7b02631.
Lim D. ; Wen X. ; Seebeck F. P. Selenoimidazolium Salts as Supramolecular Reagents for Protein Alkylation. ChemBioChem. 2020, 21 , 3515–3520. 10.1002/cbic.202000557.32779842
Kumar S. ; Helt J. P. ; Autschbach J. ; Detty M. R. A New Reaction for Organoselenium Compounds,: Alkyl Transfer from Diorganoselenium(IV) Dibromides to Alkenoic Acids To Give γ- and δ-Lactones. Organometallics 2009, 28 (12 ), 3426–3436. 10.1021/om900134p.
Xu C. ; Lu S. ; Huang X. A new synthesis of allyl ethers via allyldialkyltelluronium salts. Synth. Commun. 1993, 23 (18 ), 2527–2531. 10.1080/00397919308012585.
Xu C. ; Lu S. ; HUANG X. The reaction of allyldialkyltelluronium bromides with anilines. Heteroatom Chemistry 1994, 5 (1 ), 7–8. 10.1002/hc.520050103.
Wang K. ; Jordan J. ; Hu X.-Y. ; Wang L. Supramolecular Strategies for Controlling Reactivity within Confined Nanospaces. Angew. Chem., Int. Ed. 2020, 59 (33 ), 13712–13721. 10.1002/anie.202000045.
Ogoshi T. ; Yamagishi T.-A. ; Nakamoto Y. Pillar-Shaped Macrocyclic Hosts Pillar[n]arenes: New Key Players for Supramolecular Chemistry. Chem. Rev. 2016, 116 (14 ), 7937–8002. 10.1021/acs.chemrev.5b00765.27337002
Ogoshi T. ; Kanai S. ; Fujinami S. ; Yamagishi T. ; Nakamoto Y. para-bridged symmetrical pillar[5]arenes:: Their Lewis acid catalyzed synthesis and host-guest property. J. Am. Chem. Soc. 2008, 130 (15 ), 5022–5023. 10.1021/ja711260m.18357989
Wang K. ; Jordan J. A. ; Velmurugan K. ; Tian X. ; Zuo M. ; Hu X.-Y. ; Wang L. Role of Functionalized Pillararene Architectures in Supramolecular Catalysis. Angew. Chem., Int. Ed. 2021, 60 (17 ), 9205–9214. 10.1002/anie.202010150.
Zhang H. ; Li C. Pillararene-functionalised graphene nanomaterials. RSC Adv. 2020, 10 (31 ), 18502 10.1039/D0RA02964E.35517199
Kato K. ; Maeda K. ; Mizuno M. ; Nishina Y. ; Fa S. ; Ohtani S. ; Ogoshi T. Room-Temperature Ring-Opening Polymerization of δ-Valerolactone and ε-Caprolactone Caused by Uptake into Porous Pillar[5]arene Crystals. Angew. Chem.Int. Ed. 2022, 61 (50 ), e202212874 10.1002/anie.202212874.
Zyryanov G. V. ; Kopchuk D. S. ; Kovalev I. S. ; Santra S. ; Majee A. ; Ranu B. Pillararenes as Promising Carriers for Drug Delivery. Int. J. Mol. Sci. 2023, 24 (6 ), 5167 10.3390/ijms24065167.36982244
Wang C. ; Li H. ; Dong J. ; Chen Y. ; Luan X. ; Li X. ; Du X. Pillararene-Based Supramolecular Vesicles for Stimuli-Responsive Drug Delivery. Chem.—Eur. J. 2022, 28 (71 ), e202202050 10.1002/chem.202202050.35969026
Wang Q. ; Fan J. ; Bian X. ; Yao H. ; Yuan X. ; Han Y. ; Yan C. A microenvironment sensitive pillar[5]arene-based fluorescent probe for cell imaging and drug delivery. Chin. Chem. Lett. 2022, 33 (4 ), 1979–1982. 10.1016/j.cclet.2021.10.040.
Zhou Y. ; Wang Q. ; Ma L. ; Fan J. ; Han Y. ; Yan C. Complexation of pillar[5]arene-based Schiff bases with methylene blue: Formation of binary complexes with improved anticancer activity. J. Mol. Struct. 2022, 1257 (5 ), 132588 10.1016/j.molstruc.2022.132588.
Lou X.-Y. ; Wang J. ; Zhang G. ; Yang Y.-W. Pyrene-Armed Pillararene Nanostructure-Facilitated Enhanced Fluorescence and Self-Driven Gelation. ACS Appl. Nano Mater. 2022, 5 (10 ), 13720–13728. 10.1021/acsanm.2c00161.
Zhai M. M. ; Wu C.-Y. ; Liu Y. A. ; Hu W.-B. ; Yang H. ; Wen K. Hydroxy-Rich Pillar[5]arene-Based Nanoporous Aromatic Frameworks (PAFs) for Efficient CO2 Uptake under Ambient Conditions. ACS Appl. Nano Mater. 2022, 5 , 14221–14226. 10.1021/acsanm.2c03045.
Filimonova D. ; Nazarova A. ; Yakimova L. ; Stoikov I. Solid Lipid Nanoparticles Based on Monosubstituted Pillar[5]arenes: Chemoselective Synthesis of Macrocycles and Their Supramolecular Self-Assembly. Nanomaterials 2022, 12 (23 ), 4266 10.3390/nano12234266.36500889
Wang J. ; Zhou L. ; Bei J. ; Zhao Q. ; Li X. ; He J. ; Cai Y. ; Chen T. ; Du Y. ; Yao Y. An enhanced photo-electrochemical sensor constructed from pillar [5] arene functionalized Au NPs for ultrasensitive detection of caffeic acid. Talanta 2022, 243 , 123322 10.1016/j.talanta.2022.123322.35228106
Paudics A. ; Hessz D. ; Bojtár M. ; Bitter I. ; Horváth V. ; Kállay M. ; Kubinyi M. A pillararene-based indicator displacement assay for the fluorescence detection of vitamin B1. Sens. Actuators B-Chemical 2022, 369 , 132364 10.1016/j.snb.2022.132364.
Xiao Y. ; Huang C. ; Li H. ; Sun G. ; Tu M. ; Sun L. ; Wang F. A novel AIEE pillar[5]arene-based conjugated oligomer as paraquat fluorescence turn-off sensor. Dyes Pigm. 2023, 210 , 111027 10.1016/j.dyepig.2022.111027.
Zhu P. ; Kong L. ; Zhang Y. ; Liu Q. ; Liao X. ; Song Y. ; Yang B. Synthetic transmembrane channel molecules formed by acyclic cucurbiturils and pillararene: Tuning cation selectivity and generating membrane potential. J. Mol. Liq. 2023, 372 , 121198 10.1016/j.molliq.2023.121198.
Xin P. ; Kong H. ; Sun Y. ; Zhao L. ; Fang H. ; Zhu H. ; Jiang T. ; Guo J. ; Zhang Q. ; Dong W. ; Chen C. Artificial K+ Channels Formed by Pillararene-Cyclodextrin Hybrid Molecules: Tuning Cation Selectivity and Generating Membrane Potential. Angew. Chem.Int. Ed. 2019, 58 (19 ), 2779–2784. 10.1002/anie.201813797.
Strilets D. ; Fa S. ; Hardiagon A. ; Baaden M. ; Ogoshi T. ; Barboiu M. Biomimetic Approach for Highly Selective Artificial Water Channels Based on Tubular Pillar[5]arene Dimers. Angew. Chem., Int. Ed. 2020, 59 (51 ), 23213–23219. 10.1002/anie.202009219.
Xiao X.-D. ; Bai Y.-L. ; Liu J.-Q. ; Wang J.-W. Synthesis of novel pillar[5]arene-based N-heterocyclic carbene ligands for Pd-catalysed Heck reactions. Tetrahedron Lett. 2016, 57 (30 ), 3385–3388. 10.1016/j.tetlet.2016.06.083.
Lan S. ; Yang X. ; Shi K. ; Fan R. ; Ma D. Pillarquinone-Based Porous Polymer for a Highly-Efficient Heterogeneous Organometallic Catalysis. ChemCatChem. 2019, 11 (12 ), 2864–2869. 10.1002/cctc.201900516.
Guo H. ; Ye J. ; Zhang Z. ; Wang Y. ; Yuan X. ; Ou C. ; Ding Y. ; Yan C. ; Wang J. ; Yao Y. Pillar[5]arene-Based [2]Rotaxane: Synthesis, Characterization, and Application in a Coupling Reaction. Inorg. Chem. 2020, 59 (17 ), 11915–11919. 10.1021/acs.inorgchem.0c01752.32815726
Ogoshi T. ; Ueshima N. ; Yamagishi T.-A. An Amphiphilic Pillar[5]arene as Efficient and Substrate-Selective Phase-Transfer Catalyst. Org. Lett. 2013, 15 , 3742–3745. 10.1021/ol4016546.23815706
Wanderlind E. H. ; Liz D. G. ; Gerola A. P. ; Affeldt R. F. ; Nascimento V. ; Bretanha L. C. ; Montecinos R. ; Garcia-Rio L. ; Fiedler H. D. ; Nome F. Imidazole-Functionalized Pillar[5]arenes: Highly Reactive and Selective Supramolecular Artificial Enzymes. ACS Catal. 2018, 8 , 3343–3347. 10.1021/acscatal.8b00901.
Gomes L. S. ; Neto J. S. S. ; Leo I. ; Barbosa C. G. ; Moraes C. ; Freitas-Junior L. H. ; Rizzuti B. ; Santi C. ; Nascimento V. Ecofriendly aminochalcogenation of alkenes: a green alternative to obtain compounds with potential anti-SARS-CoV-2 activity. New J. Chem. 2023, 47 (14 ), 6591–6601. 10.1039/D2NJ06218F.
Chipoline I. C. ; Brasil B. F. A. B ; Neto J. S. S. ; Valli M. ; Krogh R. ; Cenci A. R. ; Teixeira K. F. ; Zapp E. ; Brondani D. ; Ferreira L. L. G. ; Andricopulo A. D. ; de Oliveira A. S. ; Nascimento V. Synthesis and investigation of the trypanocidal potential of novel 1,2,3-triazole-selenide hybrids. Eur. J. Org. Chem. 2022, 243 , 114687 10.1016/j.ejmech.2022.114687.
Portilho A. J. S. ; Gomes C. B. S. M. R. ; Moreira C. S. ; Forezi L. S. M. ; Cordeiro P. ; Nascimento V. ; Daniel J. P. ; Vasconcellos M. C. ; Moraes M. E. A. ; Moreira-Nunes C. F. A. ; Ferreira V. F. ; Montenegro R. C. ; da Rocha D. R. Synthesis, molecular docking, and biological activity of thioether derived from juglone in preclinical models of chronic myeloid leukemia. Comput. Toxicol. 2021, 20 , 100197 10.1016/j.comtox.2021.100197.
Nascimento V. ; Cordeiro P. S. ; Arca M. ; Marini F. ; Sancineto L. ; Braga A. L. ; Lippolis V. ; Iwaoka M. ; Santi C. Fast and easy conversion of ortho amidoaryldiselenides into the corresponding ebselen-like derivatives driven by theoretical investigations. New J. Chem. 2020, 44 (22 ), 9444–9451. 10.1039/D0NJ01605E.
Ángel A. Y. B. ; Campos P. R. O. ; Aberto E. E. Selenonium Salt as a Catalyst for Nucleophilic Substitution Reactions in Water: Synthesis of Thiocyanites and Selenocyanates. Molecules 2023, 28 (7 ), 3056 10.3390/molecules28073056.37049818
da Silva A. F. M. ; da Costa N. M. ; Fernandes T. S. ; Bessa I. A. A. ; D’Amato D. L. ; Senna C. A. ; Lohan-Codeço M. ; Nascimento V. ; Palumbo A. Jr ; Archanjo B. S. ; Pinto L. F. R. ; dos Santos T. C. ; Ronconi C. M. Responsive Supramolecular Devices Assembled from Pillar[5]arene Nanogate and Mesoporous Silica for Cargo Release. ACS Appl. Nano Mater. 2022, 5 (10 ), 13805–13819. 10.1021/acsanm.2c01408.
Silveira E. V. ; Wanderlind E. H. ; Masson A. K. ; Cordeiro P. S. ; Nascimento V. ; Affeldt R. F. ; Micke G. Molecular recognition of methamphetamine by carboxylatopillar[5]arene: drug-dependent complexation stoichiometry and insights into medical applications. New J. Chem. 2020, 44 (7 ), 2701–2704. 10.1039/C9NJ06213K.
Silveira E. V. ; Nascimento V. ; Wanderlind E. H. ; Affeldt R. F. ; Micke G. A. ; Garcia-Rio L. ; Nome F. Inhibitory and Cooperative Effects Regulated by pH in Host-Guest Complexation between Cationic Pillar[5]arene and Reactive 2-Carboxyphthalanilic Acid. J. Org. Chem. 2019, 84 (15 ), 9684–9692. 10.1021/acs.joc.9b01377.31283216
Santos E. C. S. ; dos Santos T. C. ; Fernandes T. S. ; Jorge F. L. ; Nascimento V. ; Madriaga V. G. C. ; Cordeiro P. S. ; Checca N. R. ; da Costa N. M. ; Pinto F. R. ; Ronconi C. A reversible, switchable pH-driven quaternary ammonium pillar[5]arene nanogate for mesoporous silica nanoparticles. J. Mater. Chem. B 2020, 8 (4 ), 703–714. 10.1039/C9TB00946A.31867589
Zhou Y. ; Jie K. ; Huang F. A redox-responsive selenium-containing pillar[5]arene-based macrocyclic amphiphile: synthesis, controllable self-assembly in water, and application in controlled release. Chem. Commun. 2017, 53 (59 ), 8364–8367. 10.1039/C7CC04779G.
Ma X. ; Liu D. ; Wan X. ; Zhao J. Mo(VI)-catalyzed conversion of nitriles to amides with hydrogen peroxide in ethanol. Synth. Commun. 2023, 53 (6 ), 503–510. 10.1080/00397911.2023.2178012.
Chen Y. ; Yang B. ; Li Q.-Y. ; Lin Y.-M. ; Gong L. Selectfluor®-enabled photochemical selective C(sp3)-H(sulfonyl)amidation. Chem. Commun. 2022, 59 (1 ), 118–121. 10.1039/D2CC05569D.
Ghadermazi M. ; Molaei S. Synthesis of Sm (III) Complex Immobilized in MCM-41: A New Heterogeneous Catalyst for the Facile Synthesis of 5-substituted 1H-tetrazoles via [3 + 2] Cycloaddition of Nitriles and Sodium Azide. Inorg. Chem. 2023, 147 , 110225 10.1016/j.inoche.2022.110225.
Ogoshi T. Synthesis of novel pillar-shaped cavitands ″Pillar[5]arenes″ and their application for supramolecular materials. J. Incl. Phenom. Macrocycl. Chem. 2012, 72 (3–4 ), 247–262. 10.1007/s10847-011-0027-2.
Ju H. ; Zhu C. N. ; Wang H. ; Page Z. A. ; Wu Z. L. ; Sessler J. L. ; Huang F. Paper without a Trail: Time-Dependent Encryption using Pillar[5]arene-Based Host-Guest Invisible Ink. Adv. Mater. 2022, 34 (6 ), 2108163 10.1002/adma.202108163.
Chen J.-F. ; Yin X. ; Zhang K. ; Zhao Z. ; Zhang S. ; Zhang N. ; Wang N. ; Chen P. Pillar[5]arene-Based Dual Chiral Organoboranes with Allowed Host-Guest Chemistry and Circularly Polarized Luminescence. Org. Chem. 2021, 86 (18 ), 12654–12663. 10.1021/acs.joc.1c01175.
Hua B. ; Shao L. ; Zhang Z. ; Liu J. ; Huang F. Cooperative Silver Ion-Pair Recognition by Peralkylated Pillar[5]arenes. J. Am. Chem. Soc. 2019, 141 (38 ), 15008–15012. 10.1021/jacs.9b08257.31509696
Hua B. ; Zhou W. ; Yang Z. ; Zhang Z. ; Shao L. ; Zhu H. ; Huang F. Supramolecular Solid-State Microlaser Constructed from Pillar[5]arene-Based Host-Guest Complex Microcrystals. J. Am. Chem. Soc. 2018, 140 (46 ), 15651–15654. 10.1021/jacs.8b11156.30395459
Sun C.-L. ; Peng H.-Q. ; Niu L.-Y. ; Chen Y.-Z. ; Wu L.-Z. ; Tung C.-H. ; Yang Q.-Z. Artificial light-harvesting supramolecular polymeric nanoparticles formed by pillar[5]arene-based host-guest interaction. Chem. Commun. 2018, 54 (9 ), 1117–1120. 10.1039/C7CC09315B.
Ma Y. ; Ji X. ; Xiang F. ; Chi X. ; Han C. ; He J. ; Abliz Z. ; Chen W. ; Huang F. A cationic water-soluble pillar[5]arene: synthesis and host-guest complexation with sodium 1-octanesulfonate. Chem. Commun. 2011, 47 (45 ), 12340–12342. 10.1039/c1cc15660h.
Todee B. ; Sanae P. ; Ruengsuk A. ; Janthakit P. ; Promarak V. ; Tantirungrotechai J. ; Sukwattanasinitt M. ; Limpanuparb T. ; Harding D. J. ; Bunchuay T. Switchable Metal-Ion Selectivity in Sulfur-Functionalised Pillar[5]arenes and Their Host-Guest Complexes. Chem. Asi. J. 2024, 19 (1 ), e202300913 10.1002/asia.202300913.
Shimizu T. ; Sakurai R. ; Azami Y. ; Hirabayashi K. ; Kamigata N. Isolation and Racemization Mechanism of Optically Active Benzylmethylphenyltelluronium Salts. EuroJoc 2010, 2010 (34 ), 6556–6562. 10.1002/ejoc.201000893.
Hirabayashi K. ; Nara Y. ; Yamashita Y. ; Kiyiota K.-I. ; Kamigata N. ; Shimzu T. Palladium-catalyzed Mizoroki–Heck-type reactionsof chalcogenonium trifluoromethanesulfonates. J. Sulfur Chem. 2009, 30 (3–4 ), 346–350. 10.1080/17415990902870927.
Hirabayashi K. ; Nara Y. ; Shimizu T. ; Kamigata N. Palladium-Catalyzed Mizoroki–Heck-type Reactions Using Telluronium Salts. Chem. Lett. 2004, 33 (10 ), 1280–1281. 10.1246/cl.2004.1280.
Lenardão E. J. ; Mendes S. R. ; Ferreira P. C. ; Perin G. ; Silveira C. C. ; Jacob R. G. Selenium- and tellurium-based ionic liquids and their use in the synthesis of octahydroacridines. Tetrahedron Lett. 2006, 47 (42 ), 7439–7442. 10.1016/j.tetlet.2006.08.049.
Erythropel H. C. ; Zimmerman J. B. ; de Winter T. M. ; Petitjean L. ; Melnikov F. ; Lam C. H. ; Lounsbury A. W. ; Mellor K. E. ; Janković N. Z. ; Tu Q. ; Pincus L. N. ; Falinski M. M. ; Shi W. ; Coish P. ; Plata D. ; Anastas P. The Green ChemisTREE: 20 years after taking root with the 12 principles. Green Chem. 2018, 20 (9 ), 1929–1961. 10.1039/C8GC00482J.
Molnár Á. ; Papp A. Catalyst recycling-A survey of recent progress and current status. Coord. Chem. Rev. 2017, 349 , 1–65. 10.1016/j.ccr.2017.08.011.
