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Synthesis 2004(6): 895-900
DOI: 10.1055/s-2004-815967
DOI: 10.1055/s-2004-815967
PAPER
© Georg Thieme Verlag Stuttgart · New York
Solvent-Free Indoles Addition to Carbonyl Compounds Promoted by CeCl3·7H2O-NaI-SiO2: An Efficient Method for the Synthesis of Streptindole
Further Information
Received
7 January 2004
Publication Date:
10 February 2004 (online)
Publication History
Publication Date:
10 February 2004 (online)
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Abstract
Efficient electrophilic substitution reactions of indoles with various carbonyl compounds proceed easily in solvent-free conditions using CeCl3·7H2O-NaI-SiO2 system promoter, to afford the corresponding bis(1H-indol-3-yl)alkanes in high yields. The synthetic value of the present procedure is demonstrated by the synthesis of streptindole (9), human intestinal bacteria metabolite.
Key words
addition reactions - carbonyl complexes - indoles - lanthanides - Lewis acids - natural products
- 1
Kam TS. In Alkaloids, Chemical and Biological Perspectives Vol. 4:Pelletier SW. Pergamon; Amsterdam: 1999. p.285 -
2a
Morris SA.Anderson RJ. Tetrahedron 1990, 46: 715 -
2b
Umezawa K.Ohse T.Yamamoto T.Koyano T.Takahashi Y. Anticancer Res. 1994, 14: 2413 -
2c
Bifulco G.Bruno I.Riccio R.Lavayre J.Bourdy G. J. Nat. Prod. 1995, 58: 1254 -
2d
Amino N.Ohse T.Koyano T.Umezawa K. Anticancer Res. 1996, 16: 55 -
2e
Umezawa K.Taniguchi T.Toi M.Ohse T.Isutsumi T.Yamamoto T.Koyano T.Ishizuka M. Drugs Exp. Clin. Res. 1996, 22: 35 -
2f
Irie T.Kubushirs K.Suzuki K.Tsukazaki K.Umezawa K.Nozawa S. Anticancer Res. 1999, 8: 49 -
3a
Bell R.Carmeli S.Sar N. J. Nat. Prod. 1994, 57: 1587 -
3b
Denis J.-N.Mauger H.Vallée Y. Tetrahedron Lett. 1997, 38: 8515 -
3c
Garattini E.Marzi M.Mineko T.Moretti GP.Penco A.Tinti O. Blood 2002, 100: 3719 -
4a
Chatterjee A.Manna S.Benerji J.Pascard C.Prange T.Shoolery J. J. Chem. Soc., Perkin Trans. 1 1989, 553 -
4b
Earle MJ.Fairhurst RA.Heaney H. Tetrahedron Lett. 1991, 32: 6171 -
4c
Chen D.Yu L.Wang PG. Tetrahedron Lett. 1996, 37: 4467 -
4d
Babu G.Sridhar N.Perumal PT. Synth. Commun. 2000, 30: 1609 -
4e
Yadav JS.Subba Reddy BV.Murthy ChVSR.Kumar GM.Madam Ch. Synthesis 2001, 783 -
4f
Nagarajan R.Perumal PT. Tetrahedron 2002, 58: 1229 -
4g
Ji S.-J.Zhon M.-F.Gu D.-G.Wang SY.Loh T.-P. Synlett 2003, 2077 -
5a
Roomi M.MacDonald S. Can. J. Chem. 1970, 48: 139 -
5b
Chakrabarty M.Ghosh N.Basak R.Harigaya Y. Tetrahedron Lett. 2002, 43: 4075 -
5c
Ramesh C.Banerjee J.Pal R.Das B. Adv. Synth. Commun. 2003, 345: 557 -
5d
Mahadevan A.Sard H.Gonzalez M.McKew JC. Tetrahedron Lett. 2003, 44: 4589 -
5e
Reddy AV.Ravinder K.Reddy VLN.Goud TV.Ravikanth V.Venkateswarlu Y. Synth. Commun. 2003, 33: 3687 - 6
Kobayashi S.Araki M.Yasuda M. Tetrahedron Lett. 1995, 36: 5773 - 7
Bandgar BP.Shaikh KA. Tetrahedron Lett. 2003, 44: 1959 - 8
Yadav JS.Subby Reddy BV.Sunitha S. Adv. Synth. Catal. 2003, 345: 349 - 9
Okuhara T. Chem. Rev. 2002, 102: 3641 - 10
Anastas PT.Warner JC. Green Chemistry: Theory and Practice Oxford University Press; Oxford: 1998. -
11a
Metzger JO. Angew. Chem. Int. Ed. 1998, 37: 2975 -
11b
Louppy A. Top. Curr. Chem. 1999, 206: 153 - 12
Bartoli G.Bosco M.Bellucci MC.Marcantoni E.Sambri L.Torregiani E. Eur. J. Org. Chem. 1999, 617 - 13
Bartoli G.Bosco M.Marcantoni E.Petrini M.Sambri L.Torregiani E. J. Org. Chem. 2001, 66: 9052 - 14
Tanaka K.Toda F. Chem. Rev. 2000, 100: 1025 - 15
Bartoli G.Marcantoni E.Sambri L. Synlett 2003, 2101 ; and references cited therein - 16
Bartoli G.Bartolacci M.Bosco M.Foglia G.Giuliani A.Marcantoni E.Sambri L.Torregiani E. J. Org. Chem. 2003, 68: 4594 - 18
Bartoli G.Bosco M.Giuliani A.Marcantoni E.Palmieri A.Petrini M.Sambri L. J. Org. Chem. 2004, , DOI: 10.1021/jo035542o - 19
Nishiguchi T.Kamio C. J. Chem. Soc., Perkin Trans. 1 1999, 707 - 20 The acid-catalyzed addition of indoles requires careful control of acidity to prevent side reactions such as dimerization or polymerization, see:
Okauchi T.Itonaga M.Minami T.Owa T.Kitoh K.Yoshino H. Org. Lett. 2000, 2: 1485 - 21
Corma A.Garcia H. Chem. Rev. 2003, 103: 4307 ; and references cited therein - A strongly hindered base, namely 2,6-di-tert-butyl-4-methylpyridine has been added to neutralize traces of HX, which might contaminate the reaction mixture, without deactivating the CeCl3·7H2O-NaI-SiO2 system, since dimerization of the indoles is promoted by residual HX. For the use of 2,6-di-tert-butyl-4-methylpyridine, see:
-
22a
Hollis TK.Bosnich B. J. Am. Chem. Soc. 1995, 117: 4570 -
22b
Barrett AGM.Braddock DC.Henschke JP.Walker ER. J. Chem. Soc., Perkin Trans. 1 1999, 873 -
22c
Mathieu B.Ghosez L. Tetrahedron 2002, 58: 8219 - 23
Osawa T.Namiki M.Suzuki K.Mitsuoka T. Mutat. Res. 1983, 122: 299 - 24
Osawa T.Namiki M. Tetrahedron Lett. 1983, 24: 4719 -
25a
Hogan IT.Sainsbury M. Synthesis 1984, 872 -
25b
Chalaye-Manger H.Denis J.-N.Averbuch-Pouchot T.Vallée Y. Tetrahedron 2000, 56: 791 - 26
Bartoli G.Bosco M.Dalpozzo R.Marcantoni E.Massaccesi M.Sambri L. Synlett 2003, 39 - 27
Meng J.-B.Du D.-M.Xiong G.-X.Wang W.-G.Wang Y.-M. J. Heterocycl. Chem. 1994, 31: 121 - 28
Xie W.Bloomfield KM.Jin NY.Wang PG. Synlett 1999, 498
References
In our methodology of Lewis acid promoted solvent-free reaction the term ‘solvent-free’ refers solely to the reaction itself. On the other hand, preparation of initial adsorbate and purification of products invariably involve the use of solvent.