Synlett 2013; 24(9): 1025-1031
DOI: 10.1055/s-0032-1318501
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© Georg Thieme Verlag Stuttgart · New York

How to ‘Cope’ with the Prenylation of the Indole C4 Position

Darius D. Schwarzer
Department of Chemistry, Institute of Organic Chemistry, Leibniz University of Hannover, Schneiderberg 1, 30167 Hannover, Germany   Fax: +43(511)7623011   Email: tanja.gaich@oci.uni-hannover.de
,
Philipp J. Gritsch
Department of Chemistry, Institute of Organic Chemistry, Leibniz University of Hannover, Schneiderberg 1, 30167 Hannover, Germany   Fax: +43(511)7623011   Email: tanja.gaich@oci.uni-hannover.de
,
Tanja Gaich*
Department of Chemistry, Institute of Organic Chemistry, Leibniz University of Hannover, Schneiderberg 1, 30167 Hannover, Germany   Fax: +43(511)7623011   Email: tanja.gaich@oci.uni-hannover.de
› Author Affiliations
Further Information

Publication History

Received: 16 January 2013

Accepted after revision: 07 March 2013

Publication Date:
11 April 2013 (online)


Abstract

Evidence supporting an enzyme-catalyzed [3,3]-sigmatropic rearrangement of the dimethallylltryptophan synthase is highlighted. A bioinspired system is discussed, by which the chemical feasibility of Cope rearrangement to the 4-position of the indole nucleus was accomplished. Furthermore, synthesis of the tricyclic benzo[cd]indole core of welwitindolinones and dragmacidine E is presented.

 
  • References and Notes

    • 1a Steffan N, Grundmann A, Yin W.-B, Kremer A, Li S.-M. Curr. Med. Chem. 2009; 16: 218
    • 1b Li S.-M. Nat. Prod. Rep. 2010; 27: 57
    • 1c Williams RM, Stocking EM, Sanz-Cervera JF. Top. Curr. Chem. 2000; 209: 97
    • 1d Edwards DJ, Clifford CL, Do KV. Abstracts of Papers, 232nd ACS National Meeting, San Francisco, CA. American Chemical Society; Washington DC: 2006: CHED-215
    • 1e Edwards DJ, Gerwick WH. J. Am. Chem. Soc. 2004; 126: 11432
    • 1f Read JA, Walsh CT. J. Am. Chem. Soc. 2007; 129: 15762
    • 1g Scott TA. Biochemistry of Alkaloids . Mother K, Schütte HR, Luckner M. VCH; Weinheim: 1985
  • 2 Gossauer A. Struktur und Reaktivität der Biomoleküle . Helvetica Chimica Acta; Zürich: 2006
  • 3 Lindel T, Marsch N, Adla SK. Top. Curr. Chem. 2012; 309: 67
    • 4a Shibuya M, Chou H.-M, Fountoulakis M, Hassam S, Kim S.-U, Kobayashi K, Otuska H, Rogalska E, Cassady JM, Floss HG. J. Am. Chem. Soc. 1990; 112: 297
    • 4b Kozikowski AP, Wu J.-P, Shibuya M, Floss HG. J. Am. Chem. Soc. 1988; 110: 1970
  • 5 Plieninger H, Immel H, Völkl A. Liebigs Ann. Chem. 1967; 706
    • 6a Pachlatko P, Tabacik C, Acklin W, Arigoni D. Chimia 1975; 29: 526
    • 6b Pachelatko P. PhD Thesis 1975
  • 7 Yuk LY. P, Tanner ME. J. Am. Chem. Soc. 2009; 131: 13932
    • 8a Gebler JC, Woodside AB, Poulter CD. J. Am. Chem. Soc. 1992; 114: 7354
    • 8b Tsai H.-F, Wang H, Gebler JC, Poulter CD, Schardl CL. Biochem. Biophys. Res. Commun. 1995; 216: 119
  • 9 Quian Q, Schultz AW, Moore BS, Tanner ME. Biochemistry 2012; 51: 7733
    • 10a Westermaier M, Mayr H. Org. Lett. 2006; 8: 4791
    • 10b Otero N, Mandado M, Mosquera RA. J. Phys. Chem. A 2007; 111: 5557
    • 11a Floss HG. Tetrahedron 1976; 32: 873
    • 11b Wenkert E, Sliwa H. Bioorg. Chem. 1977; 6: 443
    • 11c Seiler M.-P. PhD Dissertation No. 4574 . ETH Zürich; Switzerland: 1970
  • 12 Luk LY. P, Qian Q, Tanner ME. J. Am. Chem. Soc. 2011; 139: 12342
  • 13 Depew KM, Marsden SP, Zatorska D, Zatorski A, Bornmann WG, Danishefsky SJ. J. Am. Chem. Soc. 1999; 121: 11953

    • The structure of this intermediate is related to aza-Caisen rearrangements reported in:
    • 14a Jackson AH, Smith AE. Tetrahedron 1965; 21: 989
    • 14b Jackson AH, Naidoo B, Smith P. Tetrahedron 1968; 24: 6119
    • 14c Jackson AH, Smith P. Tetrahedron 1968; 24: 2227
    • 14d Biswas KM, Jackson AH. Tetrahedron 1969; 25: 227
    • 14e Jackson AH, Lynch PP. J. Chem. Soc., Perkin Trans. 2 1987; 1215
    • 14f Roe JM, Webster RA. B, Ganesan A. Org. Lett. 2003; 5: 2825
    • 14g Xiong X, Pirrung MC. J. Org. Chem. 2007; 72: 5832
    • 15a Sogo SG, Widlanski TS, Hoare JH, Grimshaw CE, Berchtold GA, Knowles JR. J. Am. Chem. Soc. 1984; 106: 2701
    • 15b Bartlett PA, Johnson CR. J. Am. Chem. Soc. 1985; 107: 7792
    • 15c Lee AY, Karplus PA, Ganem B, Clardy J. J. Am. Chem. Soc. 1995; 117: 3627
    • 15d Gustin DJ, Mattei P, Kast P, Wiest O, Lee L, Cleland WW, Hilvert D. J. Am. Chem. Soc. 1999; 121: 1756
    • 15e Schmid M, Hansen HJ, Schmid H. Helv. Chim. Acta 1973; 56: 105
    • 15f Inada S, Nagai K, Takayanagi Y, Okazaki M. Bull. Chem. Soc. Jpn. 1976; 49: 833
    • 15g Grundon MF, Hamblin MR, Harrison DM, Logue JN. D, Maguire M, McGrath JA. J. Chem. Soc., Perkin Trans. 1 1980; 1294
    • 15h Gorst-Allman CP, Steyn PS, Vleggaar R. J. Chem. Soc., Chem. Commun. 1982; 652
  • 16 For an uncatalyzed biosynthetic divinylcyclopropane rearrangement, see: Boland W, Pohnert G, Maier I. Angew. Chem., Int. Ed. Engl. 1995; 34: 1602
  • 17 Roe JM, Webster RA. B, Ganesan A. Org. Lett. 2003; 5: 2825
  • 18 Nyong AM, Rainier JD. J. Org. Chem. 2005; 70: 746
  • 19 Voûte N, Philip D, Slawin AM. Z, Westwood NJ. Org. Biomol. Chem. 2010; 8: 442
  • 20 Schwarzer DD, Gritsch PJ, Gaich T. Angew. Chem. Int. Ed. 2012; 51: 11514

    • For reviews, see:
    • 21a Schneider M. Angew. Chem. 1975; 87: 717
    • 21b Davies HM. L, Clark TJ, Smith HD. J. Org. Chem. 1991; 56: 3817
    • 21c De Meijere A, Schulz TJ, Kostikov RR, Graupner F, Murr T, Bielfeldt T. Synthesis 1991; 547
    • 21d Hudlicky T, Fan R, Reed JW, Gadamasetti KG. Org. React. DOI: , 10.1002/0471264180.or041.01.
    • 21e Davies HM. L, Stafford DG, Doan BD, Houser JH. J. Am. Chem. Soc. 1998; 120: 3326
    • 21f Davies HM. L. Advances in Cycloaddition . Haramata ME. JAI Press; Stamford: 1999
    • 21g Cordero FM, Vurchio C, Cicchi S, de Meijere A, Brandi A. Beilstein J. Org. Chem. 2011; 7: 298
  • 23 For the synthesis of 26, see: Song H, Yang J, Chen W, Qin Y. Org. Lett. 2006; 8: 6011
  • 24 For the preparation of 32, see: Yang J, Song H, Xiao X, Wang J, Qin Y. Org. Lett. 2006; 8: 2187
  • 25 Doyle MP, Davies SB, Hu W. Org. Lett. 2000; 2: 1145
  • 26 CCDC 881251 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via http://www.ccdc.cam.ac.uk/data_request/cif.

    • Isolation of welwitindolinones:
    • 27a Stratmann K, Moore RE, Bonjouklian R, Deeter JB, Patterson GM. L, Shaffer S, Smith CD, Smitka TA. J. Am. Chem. Soc. 1994; 116: 9935

    • For recent total syntheses of welwitindolinones, see:
    • 27b Reisman SE, Ready JM, Hasuoka A, Smith CJ, Wood JL. J. Am. Chem. Soc. 2006; 128: 1448
    • 27c Zheng P, Harmata M. Chemtracts 2007; 20: 20
    • 27d Richter JM, Ishihara Y, Masuda T, Whitefield BW, Llamas T, Pohjakallio A, Baran PS. J. Am. Chem. Soc. 2008; 130: 17938
    • 27e Allan KM, Kobayashi K, Rawal VH. J. Am. Chem. Soc. 2012; 134: 1392
    • 27f Quasdorf KW, Huters AD, Lodewyk MW, Tantillo DJ, Garg NK. J. Am. Chem. Soc. 2012; 134: 1396

      For the isolation of dragmacidine E, see:
    • 28a Capon RJ, Rooney F, Murray LM, Collins E, Sim AT. R, Rostas JA. P, Butler MS, Carroll AR. J. Nat. Prod. 1998; 61: 660

    • For a total synthesis of dragmacidine E, see:
    • 28b Feldman KS, Ngernmeesri P. Org. Lett. 2010; 12: 4502