Experimental and theoretical analysis of the reactivity and regioselectivity in esterification reactions of diterpenes (totaradiol, totaratriol, hinikione and totarolone)
DOI:
https://doi.org/10.13171/mjc64/01704101226-zeroualAbstract
Six esters have been synthesized in the acetylation, benzoylation and Baeyer-Villiger oxidation of starting materials totaradiol 1, totaratriol 2, hinikione 7 and totarolone 8. A complete theoretical study of the reaction has been carried out including highly regioselectivity induction experiments and using density functional methods B3LYP/6-31G(d). The analysis of the nucleophilic Parr functions P - k and the electrostatic potential in diterpenes 1 and 2 offered an explanation of the regioselectivity found in these reactions and in Baeyer-Villiger reaction we use transition state theory and the electrostatic potential to understand the high regioselectevity observed, we found that the regioselectivity is kinetically and thermodynamically favorable and the electronic density is located in the multi-substituted carbon.References
- J. Bellakhdar, La pharmacopée Marocaine traditionnelle [The Traditional Moroccan Pharmacopoeia]. Ibis Press,Paris (1997).
- M. Bourkhiss, M. Hnach, B. Bourkhiss, M. Ouhssine, A. Chaouch, Composition chimique et propriétés antimicrobiennes de l'huile essentielle extraite des feuilles de Tetraclinis articulata (Vahl) du Maroc, Afrique SCIENCE, 2007, 03(2), 232-242 ;
- T. A. Ibrahim, A. A. El-Hela, H. M. El-Hefnawy, A. M. Al-Taweel, S. Perveen, Chemical Composition and Antimicrobial Activities of Essential Oils of Some Coniferous Plants Cultivated in Egypt, Iranian Journal of Pharmaceutical Research, 2017, 16 (1), 328-337.
- F. Z ABI-Ayad, M ABI-Ayad, H.A Lazzouni, S.A Rebiahi, Bessiere, Antibacterial activity of essential oil extracted from leaves of Tetraclinis articulata (Vahl) Masters from Algeria flora, Journal of Microbiology and Biotechnology Research, 2011, 1 (1), 1-6.
- M. Akbli, N. Rhallabi, R. Ait Mhand, M. Akssira, and F. Mellouki, Antibacterial activity of the essential oil of sawdust of root burl wood of Tetraclinis articulata (VAHL) master of Morocco against clinical strains, International Journal of Innovation and Applied Studies, 2016, 16, 314-321.
- A. Tekaya-Karoui, N. Boughalleb, S. Hammami, H. Ben Jannet, Z. Mighri, Chemical composition and antifungal activity of volatile components from woody terminal branches and roots of Tetraclinis articulate (Vahl.) Masters growing in Tunisia, African Journal of Plant Science, 2011, 5(2), 115-122.
- A. Ben Ghnaya et al, traclinis articulata (Vahl.) Masters essential oil from Tunisia:Chemical characterization and herbicidal and antifungal activitiesassessment, Industrial Crops and Products, 2016, 83, 113-117
- M. El Jemli, et al, Chemical composition, acute toxicity, antioxidant and anti-inflammatory activities of Moroccan Tetraclinis articulata L, Journal of Traditional and Complementary Medicine, 2016, 1-7.
- O. Aissi, M.Boussaid, C. Messaoud, Essential oil composition in natural populations of Pistacia lentiscus L.from Tunisia: Effect of ecological factors and incidence on antioxidantand antiacetylcholinesterase activities, Industrial Crops and Products, 2016, 91, 56-65
- A. Djouahri, et al, Inhibitory effect on corrosion of carbon steel in acidic media, antioxidant, antimicrobial, anti-5-lipooxygenase and anti-xanthine oxidase activities of essential oil from Tetraclinis articulata (Vahl) Masters leaves, Journal of Essential Oil Research, 2016, 1-10;
- A. E. Koepp, et al, Cyclization of geranylgeranyl diphosphate to txa-4(5), 11(12)-diene is the committedstep of taxol biosynthesis in pacific yew, J. Biol. Chem. 1995, 270, 8686-8690.
- H. H. Higa, C.Butor, S. Diaz and A. Varki, O-acetylation and de-O-acetylation of sialic acids. O-acetylation of sialic acids in the rat liver Golgi apparatus involves an acetyl intermediate and essential histidine and lysine residues--a transmembrane reaction? J. Biol. Chem. 1989, 264, 19427-19434.
- P. Phukan, Iodine as an extremely powerful catalyst for the acetylation of alcohols under solvent-free conditions, Tetra Letters, 2004, 45, 4785-4787.
- A. R. Gholap, K. Venkatesan, T. Daniel, R. J. Lahoti, K. V. Srinivasan, Ultrasound promoted acetylation of alcohols in room temperature ionic liquid under ambient conditions, Green Chem. 2003, 5, 693-696.
- L. R. Domingo, M. J. Aurell, M. N. Kneeteman, P. M. Mancini, Mechanistic details of the Domino Reaction of Nitronaphthalenes with the Electron-rich Dienes. A DFT study, J. Mol. Struct. 2008, 853, 68-76.
- Y. Zhao, D.G. Truhlar, Hybrid Meta Density Functional Theory Methods for Thermochemistry, Thermochemical Kinetics, and Noncovalent Interactions: The MPW1B95 and MPWB1K Models and Comparative Assessments for Hydrogen Bonding and van der Waals Interactions, J. Phys. Chem. A, 2004, 108, 6908 -6918.
- H.B. Schlegel, Optimization of Equilibrium Geometries and Transition Structures, J. Comput. Chem. 1982, 2, 214 218.
- M.J. Frisch et al., Gaussian 09, Revision A 02, Gaussian Inc., Wallingford CT, 2009.
- R.G. Parr,.L. V.; Szentpaly, S. Liu, Electrophilicity Index, J. Am. Chem. Soc. 121 (1999) 1922-1924.
- R.G. Parr, R.G. Pearson, Absolute Hardness: Companion Parameter to Absolute Electronegativity, J. Am. Chem. Soc. 1983, 105, 7512 -7516.
- P. Jaramillo, L.R. Domingo, E. Chamorro, P. Pérez, further exploration of a nucleophilicity index based on the gas-phase ionization potentials J. Mol. Struct. 2008, 865, 68-72.
- W. Kohn, L.Sham, Self-Consistent Equations Including Exchange and Correlation Effects, J. Phys. Rev. 1965, 140, 1133-1138.
- A. Zeroual, A. Benharref, A. El Hajbi, Theoretical study of stereoselectivity of the [1+2] cycloaddition reaction between (1S,3R,8S)-2,2-dichloro-3,7,7,10-tetramethyltricyclo[6,4,0,01.3]dodec-9-ene and dibromocarbene using density functional theory (DFT) B3LYP/6-31G*(d), J Mol Model, 2015, 21, 2594-2599.
- A. Zeroual, A. El Haib, A. Benharref, A. El Hajbi, A combined experimental and theoretical study of highly chemioselectivity acetylation of diterpene, JCMMDA. 2015, 5, 58-62.
- A. Zeroual, M. Zoubir, R. Hammal, A. Benharref, A. El Hajbi, Understanding the regioselectivity and reactivity of Friedel-Crafts benzoylation using Parr functions, Mor. J. Chem. 2015, 3, 356-360.
- L. R. Domingo, M. J. Aurell, P. Pérez, A mechanistic study of the participation of azomethine ylides and carbonyl ylides in [3+2] cycloaddition reactions, Tetrahedron 2015, 71, 1050-1057.
- M. Zoubir, A. Zeroual, M. El Idrissi, A. El Haib, M. Moumou, R. Hammal, N. Mazoir, A. Benharref, A. El Hajbi, Journal of Materials and Environmental Sciences, 2017, 8, 990-996.
- N. Ourhriss, A. Zeroual, M. Ait Elhad, N. Mazoir, A. Abourriche, C. A. Gadhi, A. Benharref, A. El Hajbi, Synthesis of 1-isopropyl-4,7-dimethyl-3-nitronaphthalene: An experimental and theoretical study of regiospecific nitration, Journal of Materials and Environmental Sciences, 2017, 8 (4) 1385-1390.
- K. Fukui, Formulation of the reaction coordinate, J. Phys. Chem., 1970, 74, 4161-4163.
- J. Tomasi and M. Persico, Molecular Interactions in Solution: An Overview of Methods Based on Continuous Distributions of the Solvent, Chem. Rev., 1994, 94, 2027-2094.
- L.R. Domingo, J.A. Sáez, Understanding the mechanism of polar Diels-Alder reactions, Org. Biomol. Chem. 2009, 7, 3576-3583.
- L.R. Domingo, P. Pérez, J. A. Sáez, Understanding the regioselectivity in hetero Diels-Alder reactions. An ELF analysis of the reaction between nitrosoethylene and 1-vinylpyrrolidine, Tetrahedron, 2013, 69, 107-114.
- L. R. Domingo, E. Chamorro, P. Perez., Understanding the Reactivity of Captodative Ethylenes in Polar Cycloaddition Reactions. A Theoretical Study. J. Org. Chem. 2008, 73, 4615 -4624.
- L.R. Domingo, P. Pérez, The nucleophilicity N index in organic chemistry, Org. Biomol. Chem. 2011, 9, 7168-7175.
- L.R. Domingo, M. J. Aurell, P. Pérez, R. Contreras, Quantitative characterization of the global electrophilicity power of common diene/dieniphile pairs in Diels-Alder reactions. Tetrahedron, 2002, 58, 4417-4423.
- L.R. Domingo, M.J. Aurell, P. Pérez, R. Contreras, Quantitative Characterization of the Local Electrophilicity of Organic Molecules. Understanding the Regioselectivity on Diels-Alder Reactions, J. Phys. Chem. A, 2002, 106, 6871 -6875.
- R.F. Stewart, On the mapping of electrostatic properties from Bragg diffraction data, Chem. Phys. Lett. 1979, 65, 335-342
- J.S. Murray, P. Politzer, The electrostatic potential: an overview, WIREs Comp. Mol. Sci. 2011, 1, 153-163.
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