Iodocyclization of Diallyl-Dihydroxy Naphthalenes Using N-Iodosuccinimide vs Molecular Iodine in Aqueous Micelle

DOI: 10.4236/ijoc.2013.33022   PDF   HTML     4,121 Downloads   6,199 Views   Citations


A number of doubly-fused [1,2] naphthodifurans have been synthesized from the corresponding diallyl-dihydroxy naphthalene precursors involving N-iodosuccinimide in acetonitrile and also by molecular iodine in aqueous micelle using CTAB as surfactant. The electrophilic cyclization occurs regioselectively by a 5-exo-trig mode of cyclization.

Share and Cite:

P. Basu and A. Ghosh, "Iodocyclization of Diallyl-Dihydroxy Naphthalenes Using N-Iodosuccinimide vs Molecular Iodine in Aqueous Micelle," International Journal of Organic Chemistry, Vol. 3 No. 3, 2013, pp. 176-184. doi: 10.4236/ijoc.2013.33022.

Conflicts of Interest

The authors declare no conflicts of interest.


[1] S. Vincent, S. Chen, D. B. Wilson and B. Ganem, “Probing the Overlap of Chorismate Mutase and Prephenate Dehydrogenase Sites in the escherichia coli T-Protein: A Dehydrogenase-Selective Inhibitor,” Bioorganic & Medicinal Chemistry Letters, Vol. 12, No. 6, 2002, pp. 929-931. doi:10.1016/S0960-894X(02)00053-7
[2] D. M. Schultz, J. A. Prescher, S. Kidd, D. Marona-Lewicka, D. E. Nichols and A. Monte, “‘Hybrid’ benzofuran-benzopyran congeners as rigid analogs of hallucinogenic phenethylamines,” Bioorganic & Medicinal Chemistry Letters, Vol. 16, No. 11, 2008, pp. 6242-6251. doi:10.1016/j.bmc.2008.04.030
[3] C. S. Goksu, Uguz, M. T. Uguz, H. Ozdemir and H. A. Secen, “Concise Synthesis and the Antibacterial Activity of 5,6-Dimethoxy Naphthalene-2-Carboxylic Acid,” Turkish Journal of Chemistry, Vol. 29, No. 2, 2005, pp. 199-205.
[4] T. R. Burke, M. R. Fesen, A. Mazumder, J. Wang, A. M. Carothers, D. Grunberger, J. Driscoll, K. Kohn and Y. Pommier, “Hydroxylated Aromatic Inhibitors of HIV-1 Integrase,” Journal of Medicinal Chemistry, Vol. 38, No. 21, 1995, pp. 4171-4178. doi:10.1021/jm00021a006
[5] T. R. Burke, B. Lim, V. E. Marquez, Z. H. Li, J. B. Bolen, I. Stefanova and I D. Horak, “Bicyclic Compounds as Ring-Constrained Inhibitors of Protein-Tyrosine Kinase p56lck,” Journal of Medicinal Chemistry, Vol. 36, No. 4, 1993, pp. 425-432.doi:10.1021/jm00056a001
[6] K. Carl and L. U. S. Joseph, Patent 4,073,912, Chemical Abstracts, 19 78, 89, 24156, 1972.
[7] S. Rizzo, C. Riviere, L. Piazzi, A. Bisi, S. Gobbi, M. Bartolini, V. Andrisano, F. Morroni, A. Tarozzi, J.-P. Monti and A. Rampa, “Benzofuran-Based Hybrid Compounds for the Inhibition of Cholinesterase Activity, β Amyloid Aggregation, and Aβ Neurotoxicity,” Journal of Medicinal Chemistry, Vol. 51, No. 10, 2008, pp. 2883-2886. doi:10.1021/jm8002747
[8] C. Kirilmis, M. Ahmedzade, S. Servi, M. Koca, A. Kizirgil and C. Kazaz, “Synthesis and antimicrobial activity of some novel derivatives of benzofuran: Part 2. The synthesis and antimicrobial activity of some novel 1-(1-benzofuran-2-yl)-2-mesitylethanone derivatives,” European Journal of Medicinal Chemistry, Vol. 43, No. 2, 2008, pp. 300-308. doi:10.1016/j.ejmech.2007.03.023
[9] K. Ando, Y. Kawamura, Y. Akai, J. Kunitomo, T. Yokomizo, M. Yamashita, S. Ohta, T. Ohishi and Y. Ohishi, “Preparation of 2-,3-,4-and 7-(2-Alkylcarbamoyl-1-al-kylvinyl)Benzo [b] Furans and Their BLT1 and/or BLT2 Inhibitory Activities,” Organic & Biomolecular Chemistry, Vol. 6, No. 2, 2008, pp. 296-307. doi:10.1039/b710935k
[10] M. Ettaoussi, B. Peres, D. Klupsch, P. Delagrange, J.-A. Boutin, P. Renard, D.-H. Caignard, P. Chavatte, P. Berthelot, D. Lesieur and S. Yous, “ Design and Synthesis of Benzofuranic Derivatives as New Ligands at the Melatonin-Binding Site MT3,” Bioorganic & Medicinal Chemistry, Vol. 16, No. 9, 2008, pp. 4954-4962. doi:10.1016/j.bmc.2008.03.036
[11] Y.-K. Lee, M.-H. Woo, C.-H. Kim, Y. Kim, S.-H. Lee, B.-S. Jeong, H.-W. Chang and J.-K. Son, “Two New Benzofurans from Gastrodia Elata and Their DNA Topoisomerases I and II Inhibitory Activities,” Planta Medica, Vol. 73, No. 12, 2007, pp. 1287-1291. doi:10.1055/s-2007-981619
[12] K. Oda, Y. Yamaguchi, T. Yoshimura, K. Wada and N. Nishizono, “Synthetic Models Related to Furanocoumarin-CYP 3A4 Interactions. Comparison of Furanocoumarin, Coumarin, and Benzofuran Dimers as Potent Inhibitors of CYP3A4 Activity,” Chemical and Pharmaceutical Bulletin, Vol. 55, No. 9, 2007, pp.1419-1421. doi:10.1248/cpb.55.1419
[13] G. F. Filzen, L. Bratton, X.-M. Cheng, N. Erasga, A. Geyer, C. Lee, G. Lu, J. Pulaski, R. J. Sorenson, P. C. Unangst, B. K. Trivedi and X. Xu, “Synthesis and SAR of Selective Benzothiophene, Benzofuran, and Indole-Based Peroxisome Proliferator-Activated Receptor δ Agonists,” Bioorganic & Medicinal Chemistry Letters, Vol. 17, No. 13, 2007, pp. 3630-635. doi:10.1016/j.bmcl.2007.04.047
[14] M. Useglio, P. M. Castellano, M. A. Operto, R. Torres and T. S. Kaufman, “Synthesis of 3H-Spiro-[benzofuran-2,1’-cyclohexane] Derivatives from Naturally Occurring Filifolinol and Their Classical Complement Pathway Inhibitory Activity,” Bioorganic & Medicinal Chemistry Letters, Vol. 16, No. 19, 2006, pp. 5097-5101. doi:10.1016/j.bmcl.2006.07.029
[15] H. J. Patel, J. Sarra, F. Caruso, M. Rossi, U. Doshi and R. A. Stephani, “Synthesis and Anticonvulsant Activity of New N-1’,N-3’-Disubstituted-2’H,3H,5’H-Spiro-(2-benzofuran-1,4’-imidazolidine)-2’,3,5’-triones,” Bioorganic & Medicinal Chemistry Letters, Vol. 16, No. 17, 2006, pp. 4644-4647. doi:10.1016/j.bmcl.2006.05.102
[16] J. S. Lazo, R. Nunes, J. J. Skoko, P. E. Q. de Oliveira, A. Vogt and P. Wipf, “Novel Benzofuran Inhibitors of Human Mitogen-Activated Protein Kinase Phosphatase-1,” Bioorganic & Medicinal Chemistry Letters, Vol. 14, No. 16, 2006, pp. 5643-5650. doi:10.1016/j.bmc.2006.04.036
[17] K. C. Majumdar and S. Mondal, “A New Strategy For The Synthesis Of Coumarinand Quinolone-Annulated Pyrroles via Pd(0)-Mediated Cross Coupling Followed by Cu(I)-Catalyzed Heteroannulation,” Tetrahedron Letters, Vol. 49, No. 15, 2008, pp. 2418-2420. doi:10.1016/j.tetlet.2008.02.044
[18] K. C. Majumdar, S. Mondal and N. De, “Synthesis of Cyclic Sulfonamides via Pd-Catalyzed Intramolecular Coupling Reaction: An Expedient Approach to Polycyclic Sultams,” Synlett, No. 18, 2008, pp. 2851-2855. doi:10.1055/s-0028-1083502
[19] K. C. Majumdar, S. Mondal, D. Ghosh and B. Chattopadhyay, “Concise Synthesis of Pyrimido-azocine Derivatives via Aza-Claisen Rearrangement and Intramolecular Heck Reaction,” Synthesis, Vol. 2010, No. 8, 2010, pp. 1315-1320.
[20] K. C. Majumdar, S. Mondal and D. Ghosh, “Concise Access to Pyrimidine-Annulated Azepine and Azocine Derivatives by Ru-Catalyzed Ring-Closing Metathesis,” Synthesis, Vol. 2010, No. , 2010, pp. 1176-1180.
[21] K. C. Majumdar, S. Mondal and D. Ghosh, “Synthesis of Tricyclic and Tetracyclicsultones by Pd-Catalysed Intramoleclar Cyclisation,” Tetrahedron Letters, Vol. 50, No. 33, 2009, pp. 4781-4784. doi:10.1016/j.tetlet.2009.06.028
[22] K. C. Majumdar, S. Mondal and N. De, “Synthesis of Polycyclic Sultams by Pd-Catalyzed Intramolecular Cyclization,” Synthesis, No. 18, 2009, pp. 3127-3135. doi:10.1055/s-0029-1216888
[23] K. C. Majumdar, S. Chakravorty and N. De, “Palladium-Mediated bis-and tris-biaryl Heck Coupling for the Synthesis of Heterocycles,” Tetrahedron Letters, Vol. 49, No. 21, 2008, pp. 3419-3422. doi:10.1016/j.tetlet.2008.03.118
[24] K. C. Majumdar, B. Chattopadhyay and S. Chakravorty, “An Expedient Palladium-Mediated Intramolecular Cyclization Route to the Synthesis of Bis-Fused Benzofuran and a Two-Directional Ring Closing Metathesis for the Synthesis of Bis-Oxepin and Bis-Benzoxocine,” Synthesis, Vol. 2009, pp. 674-680.
[25] B. J. Shorthill and T. E. Glass, “Naphthalene Based Calixarenes: Unusual Regiochemistry of a Friedel-Crafts Alkylation,” Organic Letters, Vol. 3, No. 4, 2001, pp. 577-579. doi:10.1021/ol006980+
[26] K. C. Majumdar, U. K. Kundu, U. Das, N. K. Jana and B. Roy, “N-Iodosuccinimide—An Effective Reagent for Regioselective Heterocyclization of o-cyclohex-2-enylanilines for the Synthesis of hexahydrocarbazoles,” Canadian Journal of Chemistry, Vol. 83, No. 1, 2005, pp. 63-67. doi:10.1139/v04-162
[27] K. C. Majumdar, P. K. Basu and B. Roy, “N-Iodosuccinimide-an Efficient Reagent for Regioselective Heterocyclization of 3-Allyl-4hydroxy[1]benzopyran-2-ones,” Synthetic Communications, Vol. 33, No. 20, 2003, pp. 3621-3630. doi:10.1081/SCC-120024750
[28] K. C. Majumdar and P. K. Basu, “N-Iodosuccinimide-mediated Regioselective Cyclization of o-cyclohex-2-enylphenols,” Synthetic Communications, Vol. 32, No. 24, 2002, pp. 3719-3724. doi:10.1081/SCC-120015388
[29] K. C. Majumdar and S. Sarkaroc, “N-Iodosuccinimide Mediated Regioselective Heterocyclization of 3-Cyclohex-2’-enyl-4-hydroxycoumarin,” Tetrahedron, Vol. 58, No. 42, 2002, pp. 8501-8504. doi:10.1016/S0040-4020(02)01024-4
[30] A. K. Yadav, B. K. Sing, N. Sing and R. P. Tripathi, “An Elegant and Unprecedented Approach to 2-methylbenzofurans,” Tetrahedron Letters, Vol. 48, No. 17, 2007, pp. 6628-6632. doi:10.1016/j.tetlet.2007.07.118
[31] M. Fousteris, C. Chevrin, J. L. Bras and J. Muzart, “Water-Promoted Iodocyclisation of 2-Allylphenols,” Green Chemistry, Vol. 8, No. 6, 2006, pp. 522-523. doi:10.1039/b602398c
[32] V. A. Mahajan, P. D. Shinde, A. S. Gajare, M. Karthikeyan and R. D. Wakharkar, “EPZ-10 Catalyzed Regioselective Transformation of Alkenes into β-Iodo Ethers, Iodohydrins and 2-Iodomethyl-2,3-dihydro Benzofurans,” Green Chemistry, Vol. 4, No. 4, 2002, pp. 325-327. doi:10.1039/b202725a
[33] A. S. Gajare, M. S. Shingare and B. P. Bandgaer, “Selective Transdithio acetalization of Acetals, Ketals, Oxathioacetals and Oxathioketals Catalyzed by Envirocat EPZ10,” Journal of Chemical Research (S), No. 8, 1998, pp. 452-453.
[34] K. C. Majumdar, A. Biswas and P. P. Mukhopadhyay, “Stannic Chloride-Iodine: An Efficient Reagent for Regioselective Synthesis of Furan Fused Heterocycles,” Synthetic Communications, Vol. 37, No. 17, 2007, pp. 2881-2890. doi:10.1080/00397910701470982
[35] K. C. Majumdar and N. Kundu, “Effect of Substitution in Stannic Chloride-Mediated Heterocyclization of 4-Allyl3-hydroxyquinoline 2(1H) ones,” Synthetic Communications, Vol. 36, No. 21, 2006, pp. 3191-3201. doi:10.1080/00397910600908892
[36] K. C. Majumdar, A. Biswas and P. P. Mukhopadhyay, “SnCl4-I2 Mediated Regioselective 6-Endo and 5-ExoCyclisation of Ortho-Allylenols,” Canadian Journal of Chemistry, Vol. 83, No. 12, 2005, pp. 2046-2051. doi:10.1139/v05-212
[37] S. H. Mashraqui, S. Kumar and C. D. Mudaliar, “Aqueous Micellar Medium in Organic Synthesis: Alkylations and Michael Reactions of Benzotriazole,” Bulletin of the Chemical Society of Japan, Vol. 74, No. 11, 2001, pp. 2133-2138. doi:10.1246/bcsj.74.2133
[38] P. V. Shinde, A. H. Kategaonkar, B. B. Shingate and M. S. Shingare, “Surfactant Catalyzed Convenient and Greener Synthesis of Tetrahydrobenzo[a]xanthene-11-Ones at Ambient Temperature,” Beilstein Journal of Organic Chemistry, Vol. 7, 2011, pp. 53-58. doi:10.3762/bjoc.7.9
[39] F. Wang, H. Liu, L. Cun, J. Zhu, J. Deng and Y. Jiang, “Asymmetric Transfer Hydrogenation of Ketones Catalyzed by Hydrophobic Metal-Amido Complexes in Aqueous Micelles and Vesicles,” The Journal of Organic Chemistry, Vol. 70, No. 23, 2005, pp. 9424-9429. doi:10.1021/jo0514826
[40] K. R. Reddy, K. C. Rajanna, S. Ramgopal, M. S. Kumar and S. Sana, “Environmentally Benign Synthetic Protocol for O-Alkylation of β-Naphthols and Hydroxy Pyridines in Aqueous Micellar Media,” Green and Sustainable Chemistry, Vol. 2, No. 4, 2012, pp. 123-132. doi:10.4236/gsc.2012.24018
[41] P. Gogoi, P. Hazarika and D. Konwar, “Surfactant/I2/Water: An Efficient System for Deprotection of Oximes and Imines to Carbonyls under Neutral Conditions in Water,” The Journal of Organic Chemistry, Vol. 70, No. 5, 2005, pp. 1934-1936. doi:10.1021/jo0480287
[42] Y.-Y. Peng, Q.-P. Ding, Z. Li, P. G. Wang and J.-P. Chenga, “Proline Catalyzed Aldol Reactions in Aqueous Micelles: An Environmentally Friendly Reaction System,” Tetrahedron Letters, Vol. 44, No. 19, 2003, pp. 3871-3875. doi:10.1016/S0040-4039(03)00692-0
[43] C. Duplais, A. Krasovskiy and B. H. Lipshutz, “Organozinc Chemistry Enabled by Micellar Catalysis. Palladium-Catalyzed Cross-Couplings between Alkyl and Aryl Bromides in Water at Room Temperature,” Organometallics, Vol. 30, No. 22, 2011, pp. 6090-6097.
[44] G.-P. Lu and C. Cai, “An Odorless and Efficient Synthesis of Symmetrical Thioethers Using Organic Halides and Thiourea in Triton X10 Aqueous Micelles,” Green Chemistry Letters and Reviews, Vol. 5, No. 3, 2012, pp. 481-485. doi:10.1080/17518253.2012.668221
[45] K. C. Majumdar, D. Ghosh and S. Mondal, “A Green Synthesis of Angularly Fused Furano-Pyrone/Coumarin and Quinolone Derivatives via Molecular Iodine-Mediated 5-exo-trig Cyclization in Aqueous Micelles,” Synthesis, Vol. 2011, No. 4, 2011, pp. 599-602. doi:10.1055/s-0030-1258394
[46] V. K. Tandon and H. K. Maurya, “Water-Promoted Unprecedented Chemo Selective Nucleophilic Substitution Reactions of 1,4-Quinones with Oxygen Nucleophiles in Aqueous Micelles,” Tetrahedron Letters, Vol. 51, No. 29, 2010, pp. 3843-3847. doi:10.1016/j.tetlet.2010.05.071
[47] M. Shiri and M. A. Zolfigol, “Surfactant-Type Catalysts in Organic Reactions,” Tetrahedron, Vol. 65, No. 3, 2009, pp. 587-598. doi:10.1016/j.tet.2008.09.085

comments powered by Disqus

Copyright © 2020 by authors and Scientific Research Publishing Inc.

Creative Commons License

This work and the related PDF file are licensed under a Creative Commons Attribution 4.0 International License.