SYNTHESIS, CHARACTERIZATION, IN SILICO OPTIMIZATION, AND CONFORMATIONAL STUDIES OF METHYL 4-O-PIVALOYL-α-L-RHAMNOPYRANOSIDES
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Published:
Mar 7, 2022
Keywords:
Conformational study, DFT optimization, Methyl α-L-rhamnopyranoside, Pivaloyl esters, Protection-deprotection method
Main Article Content
Abstract
Considering promising biological activities of natural and synthetic rhamnopyranoside esters, we have synthesized several methyl 4-O-pivaloyl-α-L-rhamnopyranosides via selective 2,3-O-acetonide protection of methyl α-L-rhamnopyranoside (4) followed by C-4 pivaloylation, and deprotection. The synthesized 4-O-pivaloate 7 and its 2,3-di-O-esters 8a-e are characterized by spectroscopy and are optimized by using density functional theory (DFT). The free energy and bond angles thus calculated are used to establish the probable conformation(s). The 2,3-O-acetonide protected rhamnopyranosides 5-6 are found to be slightly distorted from the regular 1C4 conformation, and exist between the chair and twist-boat (skew) conformation while other pivaloyl esters 7-8a-e exist in regular 1C4 chair conformation.
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Matin, M. M., Ibrahim, M., Anisa, T. R., & Rahman, M. R. (2022). SYNTHESIS, CHARACTERIZATION, IN SILICO OPTIMIZATION, AND CONFORMATIONAL STUDIES OF METHYL 4-O-PIVALOYL-α-L-RHAMNOPYRANOSIDES. Malaysian Journal of Science, 41(1), 91–105. https://doi.org/10.22452/mjs.vol41no1.6
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Original Articles
Licensee MJS, Universiti Malaya, Malaysia. This article is an open-access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
References
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Bukowicki, J., Wawer, A., & Paradowska, K. (2015). Conformational analysis of gentiobiose using genetic algorithm search and GIAO DFT calculations with 13C CPMAS NMR as a verification method. Journal of Carbohydrate Chemistry 34(3):145-162, http://dx.doi.org/10.1080/07328303.2015.1016230
Dhavale, D. D., & Matin, M. M. (2005). Piperidine homoazasugars: Natural occurrence, synthetic aspects and biological activity study. Arkivoc, iii:110-132. https://doi.org/10.3998/ark.5550190.0006.314
Elmaidomy, A. H., Mohammed, R., Owis A. I., Hetta, M. H., AboulMagd, A. M., et al. (2020). Triple-negative breast cancer suppressive activities, antioxidants and pharmacophore model of new acylated rhamnopyranoses from Premna odorata. RSC Advances 10:10584-10598. https://doi.org/10.1039/D0RA01697G
Frisch, M. J., Trucks, G. W., Schlegel, H. B., Scuseria, G. E., Robb, M. A., Cheeseman, J. R., Scalmani, G., Barone, V., Petersson, G. A., & Nakatsuji, H. (2013). Gaussian 09, Gaussian, Inc. (Wallingford CT).
Gregurick, K. S., & Kafafi, S. A. (1999). Computation of the electronic and spectroscopic properties of carbohydrates using novel density functional and vibrational self-consistent field methods. Journal of Carbohydrate Chemistry 18(8):867-890. http://dx.doi.org/10.1080/07328309908544041
Hevey, R. (2019). Strategies for the development of glycomimetic drug candidates. Pharmaceuticals 12(2):55. https://doi.org/10.3390/ph12020055
Jacob, J. N., & Tazawa, M. (2012). Glucose–aspirin: Synthesis and in vitro anti-cancer activity studies. Bioorganic & Medicinal Chemistry Letters 22:3168-3171. https://doi.org/10.1016/j.bmcl.2012.03.053
Kabir, A. K. M. S., & Matin, M. M. (1994). Regioselective acylation of a derivative of L-rhamonse using the dibutyltin oxide method. Journal of the Bangladesh Chemical Society, 7(1):73-79.
Kabir, A. K. M. S., & Matin, M. M. (1996). Selective pivaloylation of some D-glucose derivatives. Chittagong University Studies, Part II: Science 20(2):105-111.
Kabir, A. K. M. S., & Matin, M. M. (1997). Regioselective monoacylation of a derivative of L-rhamnose. Journal of Bangladesh Academy of Sciences 21(1):83-88.
Kabir, A. K. M. S., Matin, M. M., Hossain, A., & Rahman, M. S. (2002). Synthesis and antimicrobial activities of some acylated derivatives of L-rhamnose. The Chittagong University Journal of Science 26(1&2):35-44.
Kabir, A. K. M. S., Matin, M. M., Hossain, A., & Sattar, M. A. (2003). Synthesis and antimicrobial activities of some rhamnopyranoside derivatives. Journal of the Bangladesh Chemical Society 16(2):85-93.
Kazmi, I., Rahman, M., Afzal, M., Gupta, G., Saleem, S., Afzal, O., Shaharyar, M. A., Nautiyal, U., Ahmed S., & Anwar, F. (2012). Anti-diabetic potential of ursolic acid stearoyl glucoside: A new triterpenic gycosidic ester from Lantana camara. Fitoterapia 83:142-146. https://doi.org/10.1016/j.fitote.2011.10.004
Lawandi, J., Rocheleau, S., & Moitessier, N. (2016). Regioselective acylation, alkylation, silylation and glycosylation of monosaccharides. Tetrahedron 72:6283-6319.
Liu, N., Tian, X., Ding, Z., Zhou, Y., Zhang, W., Wang, Q., Zhang, Y., Gu, Y., & Zhang, J. (2017). Synthesis of aryl α-O-L-rhamnopyranoside by two-step reaction in one pot. Journal of Carbohydrate Chemistry 36:220-234. http://dx.doi.org/10.1080/07328303.2017.1390578
Luo, X. -P., Du, L. -H., He, F., & Zhou, C. H. (2013). Controllable regioselective acylation of flavonoids catalyzed by lipase in microreactors. Journal of Carbohydrate Chemistry 32(7):450-462. http://dx.doi.org/10.1080/07328303.2013.843095
Mainal, A., Hashim, R., & Mahmood, K. H. (2001). Molecular modeling of some mono- and disaccharides. Malaysian Journal of Science 20:77-90.
Matin, M. M., Sharma, T., Sabharwal, S. G., & Dhavale, D. D. (2005). Synthesis and evaluation of glycosidase inhibitory activity of 5-hydroxy substituted isofagomine analogues. Organic & Biomolecular Chemistry 3(9):1702-1707. https://doi.org/10.1039/b418283a
Matin, M. M. (2006). N-Butylation and -acetylation of a sugar derived β-aminoester. The Chittagong University Journal of Science 30(1):35-39.
Matin, M. M., Ibrahim, M., & Rahman, M. S. (2008). Antimicrobial evaluation of methyl 4-O-acetyl-α-L-rhamnopyranoside derivatives. The Chittagong University Journal of Biological Sciences 3(1&2):33-43. http://dx.doi:org/10.3329/cujbs.v3i1.13404
Matin, M. M., & Ibrahim, M. (2010). Synthesis of some methyl 4-O-octanoyl-α-L-rhamnopyranoside derivatives. Journal of Applied Sciences Research 6(10):1527-1532.
Matin, M. M. (2014). Synthesis and antimicrobial study of some methyl 4-O-palmitoyl-α-L-rhamnopyranoside derivatives. Orbital: The Electronic Journal of Chemistry 6(1):20-28. https://doi.org/10.17807/orbital.v6i1.553
Matin, M. M., Nath, A. R., Saad, O., Bhuiyan, M. M. H., Kadir, F. A., Abd Hamid, S. B., Alhadi, A. A., Ali, M. E., & Yehye, W. A. (2016). Synthesis, PASS-predication and in vitro antimicrobial activity of benzyl 4-O-benzoyl-α-L-rhamnopyranoside derivatives. International Journal of Molecular Sciences 17(9):1412. https://doi.org/10.3390/ijms17091412
Matin, M. M., Bhuiyan, M. M. H., Kabir, E., Sanaullah, A. F. M., Rahman, M. A., Hossain, M. E., & Uzzaman, M. (2019a). Synthesis, characterization, ADMET, PASS predication, and antimicrobial study of 6-O-lauroyl mannopyranosides. Journal of Molecular Structure 1195:189-197. https://doi.org/10.1016/j.molstruc.2019.05.102
Matin, M. M., Bhattacharjee, S. C., Chakraborty, P., & Alam, M. S. (2019b). Synthesis, PASS predication, in vitro antimicrobial evaluation and pharmacokinetic study of novel n-octyl glucopyranoside Esters. Carbohydrate Research 485:107812. https://doi.org/10.1016/j.carres.2019.107812
Matin, M. M., & Chakraborty, P. (2020). Synthesis, spectral and DFT characterization, PASS predication, antimicrobial, and ADMET studies of some novel mannopyranoside esters, Journal of Applied Science & Process Engineering 7(2):572-586. https://doi.org/10.33736/jaspe.2603.2020
Matin, M. M., Chakraborty, P., Alam, M. S., Islam, M. M., & Hanee, U. (2020a). Novel mannopyranoside esters as sterol 14α-demethylase inhibitors: Synthesis, PASS predication, molecular docking, and pharmacokinetic studies. Carbohydrate Research 496:108130. https://doi.org/10.1016/j.carres.2020.108130
Matin, M. M., Roshid, M. H. O., Bhattacharjee, S. C., & Azad, A. K. M. S. (2020b). PASS Predication, antiviral, in vitro antimicrobial, and ADMET studies of rhamnopyranoside esters. Medical Research Archives 8(7):2165. https://doi.org/10.18103/mra.v8i7.2165
Matin, M. M., Hasan, M.S., Uzzaman, M., Bhuiyan, M. M. H., Kibria, S. M., Hossain, M. E., & Roshid, M. H. O. (2020c). Synthesis, spectroscopic characterization, molecular docking, and ADMET studies of mannopyranoside esters as antimicrobial agents. Journal of Molecular Structure 1222:128821. https://doi.org/10.1016/j.molstruc.2020.128821
Matin, M. M., Uzzaman, M., Chowdhury, S. A., & Bhuiyan, M. M. H. (2020d). In vitro antimicrobial, physicochemical, pharmacokinetics and molecular docking studies of benzoyl uridine esters against SARS-CoV-2 main protease. Journal of Biomolecular Structure and Dynamics. http://dx.doi.org/10.1080/07391102.2020.1850358; PMID: 33297848; PMCID: PMC7738211.
Matin, M. M., Islam, N., Siddika, A., & Bhattacharjee, S. C. (2021). Regioselective synthesis of some rhamnopyranoside esters for PASS predication, and ADMET studies. Journal of the Turkish Chemical Society Section A: Chemistry 8(1):363-374. https://doi.org/10.18596/jotcsa.829658
Noorbatcha, I., Hassan, S., Hamid, A., Hadi, A., & Awang, K. (2002). Ab-initio geometry-optimization and NMR studies of chemical constituents of Piper sarmentosum. Malaysian Journal of Science 21:143-147.
Pendrill, R., Eriksson, L., & Widmalm, G. (2014). Methyl 4-O-benzyl-α-L-rhamnopyranoside. Acta Cryst. Sect. E. https://doi.org/10.1107/S1600536814007922
Shalaby, M. A., Fronczek, F. R., & Younathan, E. S. (1994a). Structural analysis of methyl α-L-rhamnopyranoside in the solid state. Carbohydrate Research 258:267-274. https://doi.org/10.1016/0008-6215(94)84092-X
Shalaby, M. A., Fronczek, F. R., & Younathan, E. S. (1994b). Conformational features of rhamnopyranose derivatives. The molecular structure of methyl 2,3,4-tri-O-acetyl-α-L-rhamnopyranoside. Carbohydrate Research 264(2):173-180. https://doi.org/10.1016/S0008-6215(05)80003-5
Sawada, T., Hashimoto, T., Nakano, H., Shigematsu, M., Ishida. H., & Kiso, M. (2006). Conformational study of α-N-acetyl-D-neuraminic acid by density functional theory. Journal of Carbohydrate Chemistry 25(5):387-405. http://dx.doi.org/10.1080/07328300600778801
Yadav, S., Yadava, S., & Yadav, K. D. S. (2013). Purification and characterization of α-L-rhamnosidase from Penicillium corylopholum MTCC-2011. Process Biochemistry 48:1348–1354.
Zhang, J., Fu, J., Chen, X., Gu, Y., & Tang, J. (2008). 4-Nitro-phenyl alpha-L-rhamnopyranoside hemihydrate. Acta Crystallogr. Sect. E Struct. Rep. Online, 264:o714.
Awual, M. R. (2017). New type mesoporous conjugate material for selective optical copper(II) ions monitoring & removal from polluted waters. Chemical Engineering Journal 307:85-94. https://doi.org/10.1016/j.cej.2016.07.110
Bukowicki, J., Wawer, A., & Paradowska, K. (2015). Conformational analysis of gentiobiose using genetic algorithm search and GIAO DFT calculations with 13C CPMAS NMR as a verification method. Journal of Carbohydrate Chemistry 34(3):145-162, http://dx.doi.org/10.1080/07328303.2015.1016230
Dhavale, D. D., & Matin, M. M. (2005). Piperidine homoazasugars: Natural occurrence, synthetic aspects and biological activity study. Arkivoc, iii:110-132. https://doi.org/10.3998/ark.5550190.0006.314
Elmaidomy, A. H., Mohammed, R., Owis A. I., Hetta, M. H., AboulMagd, A. M., et al. (2020). Triple-negative breast cancer suppressive activities, antioxidants and pharmacophore model of new acylated rhamnopyranoses from Premna odorata. RSC Advances 10:10584-10598. https://doi.org/10.1039/D0RA01697G
Frisch, M. J., Trucks, G. W., Schlegel, H. B., Scuseria, G. E., Robb, M. A., Cheeseman, J. R., Scalmani, G., Barone, V., Petersson, G. A., & Nakatsuji, H. (2013). Gaussian 09, Gaussian, Inc. (Wallingford CT).
Gregurick, K. S., & Kafafi, S. A. (1999). Computation of the electronic and spectroscopic properties of carbohydrates using novel density functional and vibrational self-consistent field methods. Journal of Carbohydrate Chemistry 18(8):867-890. http://dx.doi.org/10.1080/07328309908544041
Hevey, R. (2019). Strategies for the development of glycomimetic drug candidates. Pharmaceuticals 12(2):55. https://doi.org/10.3390/ph12020055
Jacob, J. N., & Tazawa, M. (2012). Glucose–aspirin: Synthesis and in vitro anti-cancer activity studies. Bioorganic & Medicinal Chemistry Letters 22:3168-3171. https://doi.org/10.1016/j.bmcl.2012.03.053
Kabir, A. K. M. S., & Matin, M. M. (1994). Regioselective acylation of a derivative of L-rhamonse using the dibutyltin oxide method. Journal of the Bangladesh Chemical Society, 7(1):73-79.
Kabir, A. K. M. S., & Matin, M. M. (1996). Selective pivaloylation of some D-glucose derivatives. Chittagong University Studies, Part II: Science 20(2):105-111.
Kabir, A. K. M. S., & Matin, M. M. (1997). Regioselective monoacylation of a derivative of L-rhamnose. Journal of Bangladesh Academy of Sciences 21(1):83-88.
Kabir, A. K. M. S., Matin, M. M., Hossain, A., & Rahman, M. S. (2002). Synthesis and antimicrobial activities of some acylated derivatives of L-rhamnose. The Chittagong University Journal of Science 26(1&2):35-44.
Kabir, A. K. M. S., Matin, M. M., Hossain, A., & Sattar, M. A. (2003). Synthesis and antimicrobial activities of some rhamnopyranoside derivatives. Journal of the Bangladesh Chemical Society 16(2):85-93.
Kazmi, I., Rahman, M., Afzal, M., Gupta, G., Saleem, S., Afzal, O., Shaharyar, M. A., Nautiyal, U., Ahmed S., & Anwar, F. (2012). Anti-diabetic potential of ursolic acid stearoyl glucoside: A new triterpenic gycosidic ester from Lantana camara. Fitoterapia 83:142-146. https://doi.org/10.1016/j.fitote.2011.10.004
Lawandi, J., Rocheleau, S., & Moitessier, N. (2016). Regioselective acylation, alkylation, silylation and glycosylation of monosaccharides. Tetrahedron 72:6283-6319.
Liu, N., Tian, X., Ding, Z., Zhou, Y., Zhang, W., Wang, Q., Zhang, Y., Gu, Y., & Zhang, J. (2017). Synthesis of aryl α-O-L-rhamnopyranoside by two-step reaction in one pot. Journal of Carbohydrate Chemistry 36:220-234. http://dx.doi.org/10.1080/07328303.2017.1390578
Luo, X. -P., Du, L. -H., He, F., & Zhou, C. H. (2013). Controllable regioselective acylation of flavonoids catalyzed by lipase in microreactors. Journal of Carbohydrate Chemistry 32(7):450-462. http://dx.doi.org/10.1080/07328303.2013.843095
Mainal, A., Hashim, R., & Mahmood, K. H. (2001). Molecular modeling of some mono- and disaccharides. Malaysian Journal of Science 20:77-90.
Matin, M. M., Sharma, T., Sabharwal, S. G., & Dhavale, D. D. (2005). Synthesis and evaluation of glycosidase inhibitory activity of 5-hydroxy substituted isofagomine analogues. Organic & Biomolecular Chemistry 3(9):1702-1707. https://doi.org/10.1039/b418283a
Matin, M. M. (2006). N-Butylation and -acetylation of a sugar derived β-aminoester. The Chittagong University Journal of Science 30(1):35-39.
Matin, M. M., Ibrahim, M., & Rahman, M. S. (2008). Antimicrobial evaluation of methyl 4-O-acetyl-α-L-rhamnopyranoside derivatives. The Chittagong University Journal of Biological Sciences 3(1&2):33-43. http://dx.doi:org/10.3329/cujbs.v3i1.13404
Matin, M. M., & Ibrahim, M. (2010). Synthesis of some methyl 4-O-octanoyl-α-L-rhamnopyranoside derivatives. Journal of Applied Sciences Research 6(10):1527-1532.
Matin, M. M. (2014). Synthesis and antimicrobial study of some methyl 4-O-palmitoyl-α-L-rhamnopyranoside derivatives. Orbital: The Electronic Journal of Chemistry 6(1):20-28. https://doi.org/10.17807/orbital.v6i1.553
Matin, M. M., Nath, A. R., Saad, O., Bhuiyan, M. M. H., Kadir, F. A., Abd Hamid, S. B., Alhadi, A. A., Ali, M. E., & Yehye, W. A. (2016). Synthesis, PASS-predication and in vitro antimicrobial activity of benzyl 4-O-benzoyl-α-L-rhamnopyranoside derivatives. International Journal of Molecular Sciences 17(9):1412. https://doi.org/10.3390/ijms17091412
Matin, M. M., Bhuiyan, M. M. H., Kabir, E., Sanaullah, A. F. M., Rahman, M. A., Hossain, M. E., & Uzzaman, M. (2019a). Synthesis, characterization, ADMET, PASS predication, and antimicrobial study of 6-O-lauroyl mannopyranosides. Journal of Molecular Structure 1195:189-197. https://doi.org/10.1016/j.molstruc.2019.05.102
Matin, M. M., Bhattacharjee, S. C., Chakraborty, P., & Alam, M. S. (2019b). Synthesis, PASS predication, in vitro antimicrobial evaluation and pharmacokinetic study of novel n-octyl glucopyranoside Esters. Carbohydrate Research 485:107812. https://doi.org/10.1016/j.carres.2019.107812
Matin, M. M., & Chakraborty, P. (2020). Synthesis, spectral and DFT characterization, PASS predication, antimicrobial, and ADMET studies of some novel mannopyranoside esters, Journal of Applied Science & Process Engineering 7(2):572-586. https://doi.org/10.33736/jaspe.2603.2020
Matin, M. M., Chakraborty, P., Alam, M. S., Islam, M. M., & Hanee, U. (2020a). Novel mannopyranoside esters as sterol 14α-demethylase inhibitors: Synthesis, PASS predication, molecular docking, and pharmacokinetic studies. Carbohydrate Research 496:108130. https://doi.org/10.1016/j.carres.2020.108130
Matin, M. M., Roshid, M. H. O., Bhattacharjee, S. C., & Azad, A. K. M. S. (2020b). PASS Predication, antiviral, in vitro antimicrobial, and ADMET studies of rhamnopyranoside esters. Medical Research Archives 8(7):2165. https://doi.org/10.18103/mra.v8i7.2165
Matin, M. M., Hasan, M.S., Uzzaman, M., Bhuiyan, M. M. H., Kibria, S. M., Hossain, M. E., & Roshid, M. H. O. (2020c). Synthesis, spectroscopic characterization, molecular docking, and ADMET studies of mannopyranoside esters as antimicrobial agents. Journal of Molecular Structure 1222:128821. https://doi.org/10.1016/j.molstruc.2020.128821
Matin, M. M., Uzzaman, M., Chowdhury, S. A., & Bhuiyan, M. M. H. (2020d). In vitro antimicrobial, physicochemical, pharmacokinetics and molecular docking studies of benzoyl uridine esters against SARS-CoV-2 main protease. Journal of Biomolecular Structure and Dynamics. http://dx.doi.org/10.1080/07391102.2020.1850358; PMID: 33297848; PMCID: PMC7738211.
Matin, M. M., Islam, N., Siddika, A., & Bhattacharjee, S. C. (2021). Regioselective synthesis of some rhamnopyranoside esters for PASS predication, and ADMET studies. Journal of the Turkish Chemical Society Section A: Chemistry 8(1):363-374. https://doi.org/10.18596/jotcsa.829658
Noorbatcha, I., Hassan, S., Hamid, A., Hadi, A., & Awang, K. (2002). Ab-initio geometry-optimization and NMR studies of chemical constituents of Piper sarmentosum. Malaysian Journal of Science 21:143-147.
Pendrill, R., Eriksson, L., & Widmalm, G. (2014). Methyl 4-O-benzyl-α-L-rhamnopyranoside. Acta Cryst. Sect. E. https://doi.org/10.1107/S1600536814007922
Shalaby, M. A., Fronczek, F. R., & Younathan, E. S. (1994a). Structural analysis of methyl α-L-rhamnopyranoside in the solid state. Carbohydrate Research 258:267-274. https://doi.org/10.1016/0008-6215(94)84092-X
Shalaby, M. A., Fronczek, F. R., & Younathan, E. S. (1994b). Conformational features of rhamnopyranose derivatives. The molecular structure of methyl 2,3,4-tri-O-acetyl-α-L-rhamnopyranoside. Carbohydrate Research 264(2):173-180. https://doi.org/10.1016/S0008-6215(05)80003-5
Sawada, T., Hashimoto, T., Nakano, H., Shigematsu, M., Ishida. H., & Kiso, M. (2006). Conformational study of α-N-acetyl-D-neuraminic acid by density functional theory. Journal of Carbohydrate Chemistry 25(5):387-405. http://dx.doi.org/10.1080/07328300600778801
Yadav, S., Yadava, S., & Yadav, K. D. S. (2013). Purification and characterization of α-L-rhamnosidase from Penicillium corylopholum MTCC-2011. Process Biochemistry 48:1348–1354.
Zhang, J., Fu, J., Chen, X., Gu, Y., & Tang, J. (2008). 4-Nitro-phenyl alpha-L-rhamnopyranoside hemihydrate. Acta Crystallogr. Sect. E Struct. Rep. Online, 264:o714.