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Synthetic Communications
An International Journal for Rapid Communication of Synthetic Organic Chemistry
Volume 51, 2021 - Issue 1
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Articles

A straightforward synthesis of natural oxygenated ent-kaurenoic acid derivatives

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Pages 123-133 | Received 05 Aug 2020, Published online: 21 Sep 2020

References

  • Hanson, J. R. Diterpenoids of Terrestrial Origin. Nat. Prod. Rep. 2017, 34, 1233–1243 and previous reviews. DOI: 10.1039/c7np00040e.
  • (a) Sun, H.-D.; Huang, S.-X.; Han, Q.-B. Diterpenoids from Isodon Species and Their Biological Activities. Nat. Prod. Rep. 2006, 23, 673–698. DOI: 10.1039/b604174d. (b) Liu, M.; Wang, W.-G.; Sun, H.-D.; Pu, J.-X. Diterpenoids from Isodon Species: An Update. Nat. Prod. Rep. 2017, 34, 1090–1140. DOI: 10.1039/C7NP00027H.
  • (a) Jung, H. A.; Lee, E. J.; Kim, J. S.; Kang, S. S.; Lee, J.-H.; Min, B.-S.; Choi, J. S. Cholinesterase and BACE1 Inhibitory Diterpenoids from Aralia cordata. Arch. Pharm. Res. 2009, 32, 1399–1408. DOI: 10.1007/s12272-009-2009-0. (b) Park, S. H.; Nhiem, N. X.; Kiem, P. V.; Choi, E. M.; Kim, J. A.; Kim, Y. H. A New Norlupane Triterpene from the Leaves of Acanthopanax koreanum Increases the Differentiation of Osteoblastic MC3T3-E1 Cells. Arch. Pharm. Res. 2010, 33, 75–80. DOI: 10.1007/s12272-010-2228-4. (c) Langat, M. K.; Crouch, N. R.; Pohjala, L.; Tammela, P.; Smith, P. J.; Mulholland, D. A. Ent-Kauren-19-Oic Acid Derivatives from the Stem Bark of Croton pseudopulchellus Pax. Phytochem. Lett. 2012, 5, 414–418. DOI: 10.1016/j.phytol.2012.03.002. (d) Zhu, L.; Ma, W.; Zhang, M.; Lee, M. M.-L.; Wong, W.-Y.; Chan, B. D.; Yang, Q.; Wong, W.-T.; Tai, W. C.-S.; Lee, C.-S. Scalable Synthesis Enabling Multilevel Bio-Evaluations of Natural Products for Discovery of Lead Compounds. Nat. Commun. 2018, 9, 1–10. DOI: 10.1038/s41467-018-03546-9.
  • (a) Marquina, S.; Maldonado, N.; Garduño-Ramírez, M. L.; Aranda, E.; Villarreal, M. L.; Navarro, V.; Bye, R.; Delgado, G.; Alvarez, L. Bioactive Oleanolic Acid Saponins and Other Constituents from the Roots of Viguiera decurrens. Phytochemistry 2001, 56, 93–97. DOI: 10.1016/S0031-9422(00)00283-1. (b) Tirapelli, C. R.; Ambrosio, S. R.; Da Costa, F. B.; De Oliveira, A. M. Inhibitory Action of Kaurenoic Acid from Viguiera robusta (Asteraceae) on Phenylephrine-Induced Rat Carotid Contraction. Fitoterapia 2002, 73, 56–62. DOI: 10.1016/S0367-326X(01)00365-3.
  • (a) Yang, Y.-L.; Chang, F.-R.; Wu, C.-C.; Wang, W.-Y.; Wu, Y.-C. New Ent-Kaurane Diterpenoids with anti-Platelet Aggregation Activity from Annona squamosa. J. Nat. Prod. 2002, 65, 1462–1467. DOI: 10.1021/np020191e. (b) Oliveira, B. H.; Sant'Ana, A. E. G.; Bastos, D. Z. L. Determination of the Diterpenoid, Kaurenoic Acid, in Annona glabra by HPLC. Phytochem. Anal. 2002, 13, 368–371. DOI: 10.1002/pca.670. (c) Hsieh, T. J.; Wu, Y. C.; Chen, S. C.; Huang, C. S.; Chen, C. Y. Chemical Constituents from Annona glabra. J. Chinese Chemical Soc. 2004, 51, 869–876. DOI: 10.1002/jccs.200400131. (d) Remani, B. J. P. Antitumor Constituents from Annona squamosa Fruit Pericarp. Med. Chem. Res. 2008, 17, 345–355. DOI: 10.1007/s00044-007-9070-3.
  • (a) Sartori, M. R. K.; Pretto, J. B.; Cruz, A. B.; Bresciani, L. F. V.; Yunes, R. A.; Sortino, M.; Zacchino, S. A.; Filho, V. C. Antifungal Activity of Fractions and Two Pure Compounds of Flowers from Wedelia paludosa (Acmela Brasiliensis) (Asteraceae). Pharmazie 2003, 58, 567–569. https://www.ingentaconnect.com/content/govi/pharmaz/2003/00000058/00000008/art00010?crawler=true&mimetype=application/pdf. (b) Bresciani, L. F. V.; Yunes, R. A.; Bürger, C.; De Oliveira, L. E.; Bof, K. L.; Cechinel-Filho, V. Z. Seasonal Variation of Kaurenoic Acid, a Hypoglycemic Diterpene Present in Wedelia paludosa (Acmela brasiliensis) (Asteraceae). Z. Naturforsch., C, J. Biosci. 2004, 59, 229–232. DOI: 10.1515/znc-2004-3-419. (c) Batista, R.; Braga, F. C.; Oliveira, A. B. Quantitative Determination by HPLC of Ent-Kaurenoic and Grandifl Orenic Acids in Aerial Parts of Wedelia paludosa D.C. Rev. Bras. Farmacogn. 2005, 15, 119–125. DOI: 10.1590/S0102-695X2005000200009.
  • (a) Tincusi, B. M.; Jiménez, I. A.; Bazzocchi, I. L.; Moujir, L. M.; Mamani, Z. A.; Barroso, J. P.; Ravelo, A. G.; Hernández, B. V. Antimicrobial Terpenoids from the Oleoresin of the Peruvian Medicinal Plant Copaifera paupera. Planta Med. 2002, 68, 808–812. DOI: 10.1055/s-2002-34399. (b) Costa-Lotufo, L. V.; Cunha, G. M. A.; Farias, P. A. M.; Viana, G. S. B.; Cunha, K. M. A.; Pessoa, C.; Moraes, M. O.; Silveira, E. R.; Gramosa, N. V.; Rao, V. S. N. The Cytotoxic and Embryotoxic Effects of Kaurenoic Acid, a Diterpene Isolated from Copaifera langsdorffii Oleo-Resin. Toxicon 2002, 40, 1231–1234. DOI: 10.1016/S0041-0101(02)00128-9. (c) De Alencar, C. K. M.; Paiva, L. A. F.; Santos, F. A.; Gramosa, N. V.; Silveira, E. R.; Rao, V. S. N. Smooth Muscle Relaxant Effect of Kaurenoic Acid, a Diterpene from Copaifera langsdorffii on Rat Uterus In Vitro. Phytother. Res. 2003, 17, 320–324. DOI: 10.1002/ptr.1133. (d) Cavalcanti, B. C.; Costa-Lotufo, L. V.; Moraes, M. O.; Burbano, R. R.; Silveira, E. R.; Cunha, K. M. A.; Rao, V. S. N.; Moura, D. J.; Rosa, R. M.; Henriques, J. A. P.; Pessoa, C. Genotoxicity Evaluation of Kaurenoic Acid, a Bioactive Diterpenoid Present in Copaiba Oil. Food Chem. Toxicol. 2006, 44, 388–392. DOI: 10.1016/j.fct.2005.08.011.
  • (a) Yatsuda, R.; Rosalen, P. L.; Cury, J. A.; Murata, R. M.; Rehder, V. L. G.; Melo, L. V.; Koo, H. Effects of Mikania Genus Plants on Growth and Cell Adherence of Mutans Streptococci. J. Ethnopharmacol. 2005, 97, 183–189. DOI: 10.1016/j.jep.2004.09.042. (b) Soares, A. P.; Do Nascimento, A. M.; Taleb-Contini, S. H.; De Oliveira, D. C. R. Constituents of Mikania lasiandrae. Chem. Nat. Compd. 2007, 43, 708–709. DOI: 10.1007/s10600-007-0239-2.
  • (a) Pyrek, J. St. New Pentacyclic Diterpene Acid: Trachyloban-19-Oic Acid from Sunflower. Tetrahedron 1970, 26, 5029–5032. DOI: 10.1016/S0040-4020(01)93154-0. (b) Elliger, C. A.; Zinkel, D. F.; Chan, B. G.; Waiss, A. C. Jr. Diterpene Acids as Larval Growth Inhibitors. Experientia 1976, 32, 1364–1366. DOI: 10.1007/BF01937376. (c) Bohlmann, F.; Jakupovic, J.; King, R. M.; Robinson, H. Neue Ent-Atisiren-Und Ent-Kaurensäure-Derivate Aus Helianthus-Arten. Phytochemistry 1980, 19, 863–868. DOI: 10.1016/0031-9422(80)85127-2. (d) Herz, W.; Kulanthaivel, P.; Watanabe, K. Ent-Kauranes and Other Constituents of Three Helianthus Species. Phytochemistry 1983, 22, 2021–2025. DOI: 10.1016/0031-9422(83)80036-3. (e) Mitscher, L. A.; Rao, G. S. R.; Veysoglu, T.; Drake, S.; Haas, T. Isolation and Identification of Trachyloban-19-Oic and (-)-Kaur-16-en-19-Oic Acids as Antimicrobial Agents from the Prairie Sunflower, Helianthus annuus. J. Nat. Prod. 1983, 46, 745–746. DOI: 10.1021/np50029a024. (f) Herz, W.; Kulanthaivel, P. Ent-Pimaranes, Ent-Kauranes, Heliangolides and Other Constituents of Three Helianthus Species. Phytochemistry 1984, 23, 1453–1459. DOI: 10.1016/S0031-9422(00)80485-9. (g) Morris, B. D.; Foster, S. P.; Grugel, S.; Charlet, L. D. Isolation of the Diterpenoids, Ent-Kauran-16Alpha-Ol and Ent-Atisan-16Alpha-Ol, from Sunflowers, as Oviposition Stimulants for the Banded Sunflower Moth, Cochylis hospes. J. Chem. Ecol. 2005, 31, 89–102. DOI: 10.1007/s10886-005-0976-2. (h) Macías, F. A.; López, A.; Varela, R. M.; Torres, A.; Molinillo, J. M. G. Helikauranoside A, a New Bioactive Diterpene. J. Chem. Ecol. 2008, 34, 65–69. DOI: 10.1007/s10886-007-9400-4.
  • Morarescu, O. Synthetic Transformations of Ent-Kaurenoic Acid. Chemjmold. 2015, 10, 9–19. DOI: 10.19261/cjm.2015.10(1).01.
  • (a) Ungur, N.; Grinco, M.; Kulciţki, V.; Barba, A.; Bîzîcci, T.; Vlad, P. F. Isolation of Ent-Kaur-16-en-19-Oic and Ent-Trachiloban-19-Oic Acids from the Sunflower Helianthus annuus L. Dry Waste. Chem. J. Mold 2008, 4, 106–109. DOI: 10.19261/cjm.2008.03(2).01. (b) Morarescu, O.; Grinco, M.; Dragalin, I.; Kulciţki, V.; Ungur, N. Study on Extraction Process of Sunflower (Helianthus annuus L) Dry Wastes Using Different Solvents. Chemjmold. 2013, 8, 90–93. DOI: 10.19261/cjm.2013.08(2).11.
  • (a) Hueso-Falcón, I.; Girón, N.; Velasco, P.; Amaro-Luis, J. M.; Ravelo, A. G.; de las Heras, B.; Hortelano, S.; Estevez-Braun, A. Synthesis and Induction of Apoptosis Signaling Pathway of Ent-Kaurane Derivatives. Bioorg. Med. Chem. 2010, 18, 1724–1735. DOI: 10.1016/j.bmc.2009.11.064. (b) Hueso-Falcón, I.; Cuadrado, I.; Cidre, F.; Amaro-Luis, J. M.; Ravelo, A. G.; Estevez-Braun, A.; de Las Heras, B.; Hortelano, S. Synthesis and anti-Inflammatory Activity of Ent-Kaurene Derivatives. Eur. J. Med. Chem. 2011, 46, 1291–1305. DOI: 10.1016/j.ejmech.2011.01.052. (c) Simão, M.; Carneiro, L. J.; dos Santos, R. A.; Bastos, J. K.; Veneziani, R. C. S.; Ambrósio, S. R.; Mizuno, C. S. In Vitro Cytotoxicity Study of Ent-Kaurenoic Acid Derivatives against Human Breast Carcinoma Cell Line. Med. Chem. Res. 2016, 25, 303–309. DOI: 10.1007/s00044-015-1483-9.
  • Payne, G. B. Monoperphthalic Acid. Org. Synth. Coll. 1973, 5, 805. DOI: 10.15227/orgsyn.042.0077.
  • Hanson, J. R.; Hitchcock, P. B.; Takahashi, J. A. Biotransformation of Ent-16β,19-Dihydroxykaurane by Cephalosporium Aphidicola. Phytochemistry 1995, 40, 797–800. DOI: 10.1016/0031-9422(95)00431-6.
  • (a) Batista, R.; García, P. A.; Castro, M. A.; del Corral, J. M. M.; San Feliciano, A.; de Oliveira, A. B. New Oxidized Ent-Kaurane and Ent-Norkaurane Derivatives from Kaurenoic Acid. J. Braz. Chem. Soc. 2007, 18, 622–627. DOI: 10.1590/S0103-50532007000300020. (b) Hueso-Falcón, I.; Girón, N.; Velasco, P.; Amaro-Luis, J. M.; Ravelo, A. G.; de las Heras, B.; Hortelano, S.; Estevez-Braun, A. Synthesis and Induction of Apoptosis Signaling Pathway of Ent-Kaurane Derivatives. Bioorg. Med. Chem. 2010, 18, 1724–1735. DOI: 10.1016/j.bmc.2009.11.064.
  • (a) Kulciţki, V.; Ungur, N.; Gavagnin, M.; Carbone, M.; Cimino, G. Further Synthetic Studies towards the Austrodorane Skeleton: Synthesis of Austrodoral. Eur. J. Org. Chem. 2005, 2005, 1816–1822. DOI: 10.1002/ejoc.200400795. (b) Sîrbu, T.; Girbu, V.; Harghel, P.; Rusu, V.; Ungur, N.; Kulciţki, V. Selectivity Control in Terpene Rearrangements: A Biomimetic Synthesis of the Halimanic Bicyclic Core. Synthesis 2019, 51, 1995–2000. DOI: 10.1055/s-0037-1610686.
  • (a) Yahara, S.; Ishida, M.; Yamasaki, K.; Tanaka, O.; Mihashi, S. Minor Diterpenes of Aralia cordata Thunb: 17-Hydroxy-Ent-Kaur-15-En-19-Oic Acid and Grandifloric Acid. Chem. Pharm. Bull. 1974, 22, 1629–1631. DOI: 10.1248/cpb.22.1629. (b) Dang, N. H.; Zhang, X. F.; Zheng, M. S.; Son, K. H.; Chang, H. W.; Kim, H. P.; Bae, K. H.; Kang, S. S. Inhibitory Constituents against Cyclooxygenases from Aralia cordata Thunb. Arch. Pharm. Res. 2005, 28, 28–33. DOI: 10.1007/BF02975131.
  • (a) Bohlmann, F.; Suding, H.; Cuatrecasas, J.; King, R. M.; Robinson, H. Neue Diterpene Aus Der Subtribus Espeletiinae. Phytochemistry 1980, 19, 267–271. DOI: 10.1016/S0031-9422(00)81971-8. (b) Bohlmann, F.; Suding, H.; Cuatrecasas, J.; Robinson, H.; King, R. M. Tricyclic Sesquiterpenes and Further Diterpenes from Espeletiopsis Species. Phytochemistry 1980, 19, 2399–2403. DOI: 10.1016/S0031-9422(00)91035-5.
  • Melek, F. R.; Gage, D. A.; Gershenzon, J.; Mabry, T. J. Sesquiterpene Lactone and Diterpene Constituents of Helianthus annuus. Phytochemistry 1985, 24, 1537–1539. DOI: 10.1016/S0031-9422(00)81061-4.
  • Minato, M.; Yamamoto, K.; Tsuji, J. Osmium Tetraoxide Catalyzed Vicinal Hydroxylation of Higher Olefins by Using Hexacyanoferrate(III) Ion as a Cooxidant. J. Org. Chem. 1990, 55, 766–768. DOI: 10.1021/jo00289a066.
  • (a) Wu, Y.-C.; Hung, Y.-C.; Chang, F.-R.; Cosentino, M.; Wang, H.-K.; Lee, K.-H. Identification of Ent-16 Beta, 17-Dihydroxykauran-19-Oic Acid as an Anti-HIV Principle and Isolation of the New Diterpenoids Annosquamosins A and B from Annona squamosa. J. Nat. Prod. 1996, 59, 635–637. DOI: 10.1021/np960416j. (b) Silva, E. A.; Takahashi, J. A.; Boaventura, M. A.; Oliveira, A. B. The Biotransformation of Ent-Kaur-16-En-19-Oic Acid by Rhizopus stolonifer. Phytochemistry 1999, 52, 397–400. DOI: 10.1016/S0031-9422(99)00219-8.
  • Chang, F.-R.; Yang, P.-Y.; Lin, J.-Y.; Lee, K.-H.; Wu, Y.-C. Bioactive Kaurane Diterpenoids from Annona glabra. J. Nat. Prod. 1998, 61, 437–439. DOI: 10.1021/np970497z.
  • Herz, W.; Kulanthaivel, P. Ent-Kauranes and 10α-Methyl-Eudesman-8αH,12-Olides from Wedelia calycina and Wedelia hispida. Phytochemistry 1984, 23, 2271–2275. DOI: 10.1016/S0031-9422(00)80533-6.
  • Xiong, J.; Ma, Y.; Xu, Y. Diterpenoids from Siegesbeckia pubescens. Phytochemistry 1992, 31, 917–921. DOI: 10.1016/0031-9422(92)80039-H.
  • Takahashi, J. A.; Boaventura, M. A. D.; Bayma, J. D. C.; Oliveira, A. B. Frutoic Acid, a Dimeric Kaurane Diterpene from Xylopia frutescens. Phytochemistry 1995, 40, 607–609. DOI: 10.1016/0031-9422(95)00264-8.
  • Sung, S. H.; Park, S. H.; Song, S. Y.; Lee, S. J.; Lee, H. W.; Kim, S. H.; Lee, M. A.; Yoon, I.-S.; Kim, D.-D.; Kang, S.; Sung, J.-H. Epidermal Regeneration by Ent-16α, 17-Dihydroxy-Kauran-19-Oic Acid Isolated from Siegesbeckia pubescens. Cell Prolif. 2011, 44, 527–536. DOI: 10.1111/j.1365-2184.2011.00786.x.
  • Lee, M.; Kim, S. H.; Kyoung Lee, H. K.; Cho, Y.; Kang, J.; Sung, S. H. Ent-Kaurane and Ent-Pimarane Diterpenes from Siegesbeckia pubescens Inhibit Lipopolysaccharide-Induced Nitric Oxide Production in BV2 Microglia. Biol. Pharm. Bull. 2014, 37, 152–157. DOI: 10.1248/bpb.b13-00233.
  • Ogawa, S.; Hosoi, K.; Ikeda, N.; Makino, M.; Fujimoto, Y.; Iida, T. Oxyfunctionalization Products of Terpenoids with Dimethyldioxirane and Their Biological Activity. Chem. Pharm. Bull. 2007, 55, 247–250. DOI: 10.1248/cpb.55.247.
  • (a) Kuai, Y. H.; Bi, Z. M.; Li, P.; Zhang, Y. H. A Novel Kaurane Diterpenoid from the Bark of Annona glabra Linn. Chem. Ind. Forest. Prod. 2006, 26, 13–15. (b) Qin, J. J.; Zhu, J. X.; Zhang, W. D.; Zhu, Y.; Fu, J. J.; Liu, X. H.; Jin, H. Z. A New Ent-Kaurane Type Diterpenoid Glycoside from Inula japonica Thunb. Arch. Pharm. Res. 2009, 32, 1369–1372. DOI: 10.1007/s12272-009-2004-5.
  • Fatope, M. O.; Audu, O. T.; Takeda, Y.; Zeng, L.; Shi, G.; Shimada, H.; McLaughlin, J. L. Bioactive Ent-Kaurene Diterpenoids from Annona senegalensis. J. Nat. Prod. 1996, 59, 301–303. DOI: 10.1021/np9601566.
  • Anoopkumar-Dukie, S.; Carey, J. B.; Conere, T.; O'sullivan, E.; van Pelt, F. N.; Allshire, A. Resazurin Assay of Radiation Response in Cultured Cells. Br. J. Radiol. 2005, 78, 945–947. DOI: 10.1259/bjr/54004230.

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