Abstract
Cyclodextrins are naturally occurring cyclic oligosaccharides consisting of glucose units. The main feature of cyclodextrins is the ability to accommodate various lipophilic compounds in their interior, which determines them to be popular helpers to the mankind. However, there is still a demand for new derivatives for advanced applications. Herein, we report the synthesis of β-cyclodextrin–pyrrole conjugates. Their preparation is based on an amide bond formation or copper(I)-catalysed azide-alkyne cycloaddition between β-cyclodextrin and pyrrole derivatives. The main advantage of the synthetic approach lies in the possibility to attach the substituent in β-position, because polypyrroles possessing a substituent in this position are generally more conductive than the N-substituted ones. Moreover, the presented synthetic route is general and allows tuning the properties (various types of connections and lengths) of a linker. The presented cyclodextrin–pyrrole derivatives thus open the door for new applications in the field of sensors or tissue engineering.
Similar content being viewed by others
References
Bhardwaj, V., Gumber, D., Abbot, V., Dhiman, S., Sharma, P.: Pyrrole: a resourceful small molecule in key medicinal hetero-aromatics. RSC Adv. 5, 15233–15266 (2015). https://doi.org/10.1039/c4ra15710a
Walsh, C.T., Garneau-Tsodikova, S., Howard-Jones, A.R.: Biological formation of pyrroles: nature’s logic and enzymatic machinery. Nat. Prod. Rep. 23, 517–531 (2006). https://doi.org/10.1039/b605245m
Huang, Y., Li, H., Wang, Z., Zhu, M., Pei, Z., Xue, Q., Huang, Y., Zhi, C.: Nanostructured polypyrrole as a flexible electrode material of supercapacitor. Nano Energy. 22, 422–438 (2016). https://doi.org/10.1016/j.nanoen.2016.02.047
Yuan, X., Ding, X.-L., Wang, C.-Y., Ma, Z.-F.: Use of polypyrrole in catalysts for low temperature fuel cells. Energy Environ. Sci. 6, 1105–1124 (2013). https://doi.org/10.1039/c3ee23520c
Setka, M., Drbohlavova, J., Hubalek, J.: Nanostructured polypyrrole-based ammonia and volatile organic compound sensors. Sensors. 17, 562 (2017). https://doi.org/10.3390/s17030562
Ateh, D.D., Navsaria, H.A., Vadgama, P.: Polypyrrole-based conducting polymers and interactions with biological tissues. J. R. Soc. Interface. 3, 741–752 (2006). https://doi.org/10.1098/rsif.2006.0141
Bendrea, A.-D., Cianga, L., Cianga, I.: Review paper: progress in the field of conducting polymers for tissue engineering applications. J. Biomater. Appl. 26, 3–84 (2011). https://doi.org/10.1177/0885328211402704
Mao, J., Li, C., Park, H.J., Rouabhia, M., Zhang, Z.: Conductive polymer waving in liquid nitrogen. ACS Nano. 11, 10409–10416 (2017). https://doi.org/10.1021/acsnano.7b05546
Izaoumen, N., Bouchta, D., Zejli, H., El Kaoutit, M., Stalcup, A.M., Temsamani, K.R.: Electrosynthesis and analytical performances of functionalized poly (pyrrole/beta-cyclodextrin) films. Talanta. 66, 111–117 (2005). https://doi.org/10.1016/j.talanta.2004.10.003
Shang, F., Zhou, L., Mahmoud, K.A., Hrapovic, S., Liu, Y., Moynihan, H.A., Glennon, J.D., Luong, J.H.T.: Selective nanomolar detection of dopamine using a boron-doped diamond electrode modified with an electropolymerized sulfobutylether-beta-cyclodextrin-doped poly(N-acetyltyramine) and polypyrrole composite film. Anal. Chem. 81, 4089–4098 (2009). https://doi.org/10.1021/ac900368m
Wajs, E., Fernández, N., Fragoso, A.: Supramolecular biosensors based on electropolymerised pyrrole–cyclodextrin modified surfaces for antibody detection. Analyst. 141, 3274–3279 (2016). https://doi.org/10.1039/C6AN00532B
Palanisamy, S., Thangavelu, K., Chen, S.-M., Velusamy, V., Chang, M.-H., Chen, T.-W., Al-Hemaid, F.M.A., Ali, M.A., Ramaraj, S.K.: Synthesis and characterization of polypyrrole decorated graphene/beta-cyclodextrin composite for low level electrochemical detection of mercury (II) in water. Sens. Actuators B. 243, 888–894 (2017). https://doi.org/10.1016/j.snb.2016.12.068
Řezanka, M.: Monosubstituted cyclodextrins as precursors for further use. Eur. J. Org. Chem. 2016, 5322–5334 (2016). https://doi.org/10.1002/ejoc.201600693
Řezanka, M.: Synthesis of substituted cyclodextrins. Environ. Chem. Lett. (2018). https://doi.org/10.1007/s10311-018-0779-7
Fritea, L., Gorgy, K., Le Goff, A., Audebert, P., Galmiche, L., Sandulescu, R., Cosnier, S.: Fluorescent and redox tetrazine films by host-guest immobilization of tetrazine derivatives within poly(pyrrole-beta-cyclodextrin) films. J. Electroanal. Chem. 781, 36–40 (2016). https://doi.org/10.1016/j.jelechem.2016.07.010
Deronzier, A., Moutet, J.C.: Polypyrrole films containing metal complexes: Syntheses and applications. Coord. Chem. Rev. 147, 339–371 (1996). https://doi.org/10.1016/0010-8545(95)01130-7
Trippé, G., Le Derf, F., Lyskawa, J., Mazari, M., Roncali, J., Gorgues, A., Levillain, E., Sallé, M.: Crown-tetrathiafulvalenes attached to a pyrrole or an EDOT unit: synthesis, electropolymerization and recognition properties. Chemistry. 10, 6497–6509 (2004). https://doi.org/10.1002/chem.200400303
Guernion, N.J.L., Hayes, W.: 3-and 3,4-substituted pyrroles and thiophenes and their corresponding polymers: a review. Curr. Org. Chem. 8, 637–651 (2004). https://doi.org/10.2174/1385272043370771
Jolicoeur, B., Chapman, E.E., Thompson, A., Lubell, W.D.: Pyrrole protection. Tetrahedron. 62, 11531–11563 (2006). https://doi.org/10.1016/j.tet.2006.08.071
Karsten, S., Nan, A., Turcu, R., Liebscher, J.: A new access to polypyrrole-based functionalized magnetic core-shell nanoparticles. J. Polym. Sci. Part A. 50, 3986–3995 (2012). https://doi.org/10.1002/pola.26193
Bunrit, A., Sawadjoon, S., Tsupova, S., Sjoberg, P.J.R., Samec, J.S.M.: A general route to beta-substituted pyrroles by transition-metal catalysis. J. Org. Chem. 81, 1450–1460 (2016). https://doi.org/10.1021/acs.joc.5b02581
Huisgen, R.: 1.3-dipolare cycloadditionen-ruckschau und ausblick. Angew. Chem. 75, 604–637 (1963). https://doi.org/10.1002/ange.19630751304
Kolb, H.C., Finn, M.G., Sharpless, K.B.: Click chemistry: Diverse chemical function from a few good reactions. Angew. Chem.-Int. Ed. 40, 2004–2021 (2001) https://doi.org/10.1002/1521-3773(20010601)40:11<2004::AID-ANIE2004>3.0.CO;2-5
Yadav, J.S., Reddy, B.V.S., Reddy, P.M., Srinivas, C.: Zinc-mediated Barbier reactions of pyrrole and indoles: a new method for the alkylation of pyrrole and indoles. Tetrahedron Lett. 43, 5185–5187 (2002). https://doi.org/10.1016/S0040-4039(02)00971-1
Bray, B., Mathies, P., Naef, R., Solas, D., Tidwell, T., Artis, D., Muchowski, J.: N-(triisopropylsilyl)pyrrole: a progenitor par excellence of 3-substituted pyrroles. J. Org. Chem. 55, 6317–6328 (1990). https://doi.org/10.1021/jo00313a019
Sonogashira, K., Tohda, Y., Hagihara, N.: A convenient synthesis of acetylenes: catalytic substitutions of acetylenic hydrogen with bromoalkenes, iodoarenes and bromopyridines. Tetrahedron Lett. 16, 4467–4470 (1975). https://doi.org/10.1016/S0040-4039(00)91094-3
Alvarez, A., Guzman, A., Ruiz, A., Velarde, E., Muchowski, J.: Synthesis of 3-arylpyrroles and 3-pyrrolylacetylenes by palladium-catalyzed coupling reactions. J. Org. Chem. 57, 1653–1656 (1992). https://doi.org/10.1021/jo00032a011
Tamao, K., Sumitani, K., Kumada, M.: Selective carbon–carbon bond formation by cross-coupling of grignard-reagents with organic halides-catalysis by nickel-phosphine complexes. J. Am. Chem. Soc. 94, 4374–4376 (1972). https://doi.org/10.1021/ja00767a075
Heravi, M.M., Hajiabbasi, P.: Recent advances in Kumada-Tamao-Corriu cross-coupling reaction catalyzed by different ligands. Monatshefte Chem. 143, 1575–1592 (2012). https://doi.org/10.1007/s00706-012-0838-x
Cheung, C.W., Ren, P., Hu, X.: Mild and phosphine-free iron-catalyzed cross-coupling of nonactivated secondary alkyl halides with alkynyl grignard reagents. Org. Lett. 16, 2566–2569 (2014). https://doi.org/10.1021/ol501087m
Ren, P., Vechorkin, O., Csok, Z., Salihu, I., Scopelliti, R., Hu, X.: Pd, Pt, and Ru complexes of a pincer bis(amino)amide ligand. Dalton Trans. 40, 8906–8911 (2011). https://doi.org/10.1039/c1dt10195a
Eckhardt, M., Fu, G.C.: The first applications of carbene ligands in cross-couplings of alkyl electrophiles: sonogashira reactions of unactivated alkyl bromides and iodides. J. Am. Chem. Soc. 125, 13642–13643 (2003). https://doi.org/10.1021/ja038177r
Csok, Z., Vechorkin, O., Harkins, S.B., Scopelliti, R., Hu, X.: Nickel complexes of a pincer NN(2) ligand: Multiple carbon-chloride activation of CH(2)Cl(2) and CHCl(3) leads to selective carbon-carbon bond formation. J. Am. Chem. Soc. 130, 8156–8157 (2008). https://doi.org/10.1021/ja8025938
Saito, B., Fu, G.C.: Alkyl-alkyl Suzuki cross-couplings of unactivated secondary alkyl halides at room temperature. J. Am. Chem. Soc. 129, 9602–9603 (2007). https://doi.org/10.1021/ja074008l
Corey, E.J., Fuchs, P.L.: A synthetic method for formyl→ethynyl conversion (RCHO→RC CH or RC CR′). Tetrahedron Lett. 13, 3769–3772 (1972). https://doi.org/10.1016/S0040-4039(01)94157-7
Kornblum, N., Jones, W., Anderson, G.: A new and selective method of oxidation. The conversion of alkyl halides and alkyl tosylates to aldehydes. J. Am. Chem. Soc. 81, 4113–4114 (1959). https://doi.org/10.1021/ja01524a080
Dave, P., Byun, H., Engel, R.: An improved direct oxidation of alkyl-halides to aldehydes. Synth. Commun. 16, 1343–1346 (1986). https://doi.org/10.1080/00397918608056381
Tang, W., Ng, S.-C.: Facile synthesis of mono-6-amino-6-deoxy-α-, β-, γ-cyclodextrin hydrochlorides for molecular recognition, chiral separation and drug delivery. Nat. Protoc. 3, 691–697 (2008). https://doi.org/10.1038/nprot.2008.37
Chmurski, K., Stepniak, P., Jurczak, J.: Improved synthesis of C2 and C6 monoderivatives of alpha- and beta-cyclodextrin via the click chemistry approach. Synthesis. 47, 1838–1843 (2015). https://doi.org/10.1055/s-0034-1380701
Acknowledgements
This work was supported by the Project LO1201 of the Ministry of Education, Youth and Sports in the framework of the targeted support of the “National Programme for Sustainability I” (Lukášek, Stibor, Řezanka); by the Project 16-02316Y of the Czech Science Foundation (Lukášek, Řezanka); and SGS Project No. 21176/115 of the Technical University of Liberec (Lukášek).
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Below is the link to the electronic supplementary material.
10847_2018_854_MOESM1_ESM.pdf
Supplementary data file features copies of NMR (1H, 13C) and HRMS spectra of all new pyrrole derivatives prepared. Supplementary material 1 (PDF 2277 KB)
Rights and permissions
About this article
Cite this article
Lukášek, J., Řezanková, M., Stibor, I. et al. Synthesis of cyclodextrin–pyrrole conjugates possessing tuneable carbon linkers. J Incl Phenom Macrocycl Chem 92, 339–346 (2018). https://doi.org/10.1007/s10847-018-0854-5
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10847-018-0854-5