TsOH·H₂O-Catalyzed Friedel-Crafts of Indoles of 3-Hydroxyisobenzofuran-1(3H)-One with Indoles: Highly Synthesis of 3-Indolyl-Substituted Phthalides

Hongying Tang, Xinyu Zhang, Airu Song, Zhongbiao Zhang

Tianjin Key Laboratory of Water Resources and Environment, Tianjin Normal University, Tianjin, CHINA.

DOI: 10.4236/mrc.2012.12002                

Abstract

An efficient and facile method for the synthesis of 3-indolyl-substituted phthalides by Friedel-Crafts alkylation of indoles with 3-hydroxyisobenzofuran-1(3H)-one has been developed. Using only 2 mol-% TsOH·H₂O as the catalyst, various substituted indoles can react smoothly at room temperature to give the corresponding phthalides products in good to excellent yields (up to 96%).

Keywords

Synthesis; 3-Indolyl-Substituted Phthalides; Friedel-Crafts Alkylation; 3-Hydroxyisobenzofuran-1(3H)-One; Indole

Conflicts of Interest

The authors declare no conflicts of interest.

References

[1]	T. K. Devon, A. I. Scott， In Handbook of Naturally Occurring Compounds; Academic Press: New York, Vol. 1, 1975.
[2]	J. B. John, S. C. Chou, “The structural diversity of phthalides from the Apiaceae,” J. Nat. Prod. Vol. 70, No. 5, 2007, pp. 891-900.
[3]	R. Bentley, “Mycophenolic Acid:? A One Hundred Year Odyssey from Antibiotic to Immunosuppressant,” Chem. Rev. Vol. 100, No. 10, 2000, pp. 3801-3826 and references therein.
[4]	J. G. Lei, R. Hong, S. G. Yuan, G. Q. Lin, “Nickel-Catalyzed Tandem. Reaction to Asymmetric Synthesis of Chiral Phthalides,” Synlett, No. 6, 2002, pp. 927-930.
[5]	W. W. Chen, M. H. Xu, G. Q. Lin, “Unusual heterochiral crystallization tendency of 3-arylphthalide compounds in non-racemic solution: reinvestigation on asymmetric Ni-catalyzed tandem reaction of substituted o-halobenzaldehydes,” Tetrahedron Lett. Vol. 48, No. 42, 2007, pp. 7508-7511.
[6]	B. Witulski, A. Zimmermann, N. D. Gowans, “First total synthesis of the marine illudalane sesquiterpenoid alcyopterosin E,” Chem. Commun. No. 24, 2002, pp. 2984-2985.
[7]	K. A. Dekker, T. Inagaki, T. D. Gootz, K. Kanede, E. Nomura, T. Sakakibara, S. Sakemi, Y. Sugie, Y. Yamauchi, N. Yoshikawa, N. Kojima, “CJ-12,954 and its congeners, new anti-Helicobacter pylori compounds produced by Phanerochaete velutina: fermentation, isolation, structural elucidation and biological activities,” J. Antibiot. Vol. 50, 1997, pp. 833-839.
[8]	X. W. Wang, “3-n-Butylphthalide. Cerebral antiischemic,” Drugs Future, Vol. 25, 2000, pp. 16-29.
[9]	K. Yoganathan, C. Rossant, S. Ng, Y. Huang, M. S.Butler, A. D. Buss, “10-Methoxydihydrofuscin, Fuscinarin, and Fuscin, Novel Antagonists of the Human CCR5 Receptor from Oidiodendron griseum,” J. Nat. Prod. Vol. 66, No. 8, 2003, pp. 1116-1117.
[10]	D. J. Faulkner, “Marine natural products,” Nat. Prod. Rep. Vol. 19, No. 1, 2002, pp. 1-49.
[11]	A. Kleeman, J. Engel, B. Kutscher, D. Reichert, Pharmaceutical Substances, 4th ed., Thieme: New York, 2001.
[12]	K. A. J?rgensen, “Asymmetric Friedel-Crafts reactions: catalytic enantioselective addition of aromatic and heteroaromatic C-H bonds to activated alkenes, carbonyl compounds and imines,” Synthesis. 2003, No. 7, pp. 1117-1125.
[13]	M. Bandini, A. Melloni, A. Umani-Ronchi, “Neue katalytische Methoden in der stereoselektiven Friedel-Crafts-Alkylierung, ”Angew. Chem. Int. Ed. Vol. 43, No. 5, 2004, pp. 550-556.
[14]	M. Bandini, A. Melloni, S.Tommasi, A. Umani-Ronchi, “A Journey Across Recent Advances in Catalytic and Stereoselective Alkylation of Indoles,” Synlett. 2005, pp. 1199-1122.
[15]	S. B. Tsogoeva, “Recent Advances in Asymmetric Organocatalytic 1,4-Conjugate Additions,” Eur. J. Org. Chem. Vol. 2007, No. 11, 2007, pp. 1701-1716.
[16]	W. E. Noland, J. E. Johnson, “3-(3-Indolyl)phthalides and 3-(2-Carboxy-benzyl)indoles,” J. Am. Chem. Soc. Vol. 82, No. 19, 1960, pp. 5143-5147.
[17]	C. W. Rees, C. R. Sabet, “Mechanism of the reaction of phthalaldehydic acid with indoles. Intramolecular catalysis in aldehyde reactions,” J. Chem. Soc. 1965, pp. 680-687.
[18]	H. Lin, X. W. Sun, “Highly efficient synthesis of 3-indolyl-substituted phthalides via Friedel–Crafts reactions in water,” Tetrahedron Lett. Vol. 49, No. 36, 2008, pp. 5343-5346.
[19]	H. Lin, K. S. Han, X. W. Sun, G. Q. Lin, “Synthesis of 3-Indolyl-substituted Phthalides Catalyzed by Acidic Cation Exchange Resin Amberlyst 15,” Chin. J. Org. Chem. Vol. 28, No. 8, 2008, pp. 1479-1482.
[20]	J. N. Freskos, G. W. Morrow, and G. S. Swenton, “Synthesis of functionalized hydroxyphthalides and their conversion to 3-cyano-1(3M-isobenzofuranones. The Diels-Alder reaction of methyl 4, 4-diethoxybutynoate and cyclohexadienes,” J. Org. Chem. Vol. 50, No. 6, 1985, pp. 805-810.
[21]	D. L. Comins and J. D. Brown, “Directed lithiation of tertiary .beta.-amino benzamides,” J. Org. Chem. Vol. 51, No. 19, 1986, pp. 3566-3572.
[22]	K. Shinji, N. Nobuaki, T. Koji and M. Toshiaki, “Non-cryogenic metallation of aryl bromides bearing proton donating groups: formation of a stable magne-sio-intermediate,” Tetrahedron Lett. Vol. 43, No. 41, 2002, pp. 7315-7317.
[23]	H. Yang, G. Y. Hu, J. Chen, Y. Wang and Z. H. Wang, “Sythesis, resolution, and antiplatelet activity of 3-substituted 1(3H)-isobenzofuranone,” Bioorg. Med. Chem. Lett. Vol. 17, No. 18, 2007, pp. 5210-5213.
[24]	W. Wang, X. X. Cha, J. Reiner, Y. Gao, H. L. Qiao, J. X. Shen, J. B. Chang, “Synthesis and biological activity of n-butylphthalide derivatives,” Eur. J. Med. Chem. Vol. 45, No. 5, 2010, pp. 1941-1946.
[25]	H. Baba, H. Togo, “Sulfonylamidation of alkylbenzenes at benzylic position with p-toluenesulfonamide and 1, 3-diiodo-5,5-dimethylhydantoin,” Tetrahedron Lett. Vol. 51, No. 15, 2010, pp. 2063-2066.
[26]	S. L. Zhang, Y. F. Zhao, Y. J. Liu, D. Chen, W. H. Lan, Q. L. Zhao, C. C. Dong, L. Xia, P. Gong, “Synthesis and antitumor activities of novel 1, 4-disubstituted phthalazine derivatives,” Eur. J. Med. Chem. Vol. 45, No. 8, 2010, pp. 3504-3510.
[27]	K. Q. Ling, G. Ji, H. Cai, J. H. Xu, “Dye-sensitized photooxygenations of 1, 3-isoquinolinediones,” Tetrahedron Lett. Vol. 39, No. 16, 1998, pp. 2381-2384.