Enantioselective Synthesis of
3H-Pyrrolo[1,2-a]indole-2-carbaldehydes
via an Organocatalytic Domino Aza-Michael/Aldol Condensation
Reaction

Dieter Enders; Chuan Wang; Gerhard Raabe

doi:10.1055/s-0029-1217069

PAPER

Enantioselective Synthesis of 3H-Pyrrolo[1,2-a]indole-2-carbaldehydes via an Organocatalytic Domino Aza-Michael/Aldol Condensation Reaction

Dieter Enders*, Chuan Wang, Gerhard Raabe
Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany
Fax: +49(241)8092127; e-Mail: enders@rwth-aachen.de;

Abstract

Alle Artikel dieser Rubrik

Abstract

A simple organocatalytic aza-Michael/aldol condensation domino reaction protocol opens an efficient and enantioselective entry to the tricyclic pyrrolo indole core, a characteristic structural unit of many bioactive natural products.

Key words

pyrrolo[1,2-a]indole - organocatalysis - domino reaction - aza-Michael reaction - asymmetric synthesis

Volltext

Referenzen

References

1a Dalton DR. The Alkaloids Marcel Dekker; Basel: 1979.

1b Mothes K. Schütte HR. Luckner M. Biochemistry of Alkaloids Verlag Chemie; Weinheim: .

1c Southon JW. Buckingham J. Dictionary of Alkaloids Chapmann & Hall; London: 1988.

For selected examples of pyrrolo[1,2-a]indole syntheses, see:

2a Minami T. Suganuma H. Agawa T. Chem. Lett. 1978, 285

2b Kazembe TC.-G. Taylor DA. Tetrahedron 1980, 36: 2125

2c Burgess K. Lim H.-J. Porte AM. Sulikowski GA. Angew. Chem., Int. Ed. Engl. 1996, 35: 220 ; Angew. Chem. 1996, 108, 192

2d Yavari I. Adib M. Sayahi MH. J. Chem. Soc., Perkin Trans. 1 2002, 1517

2e Kim M. Vedejs E. J. Org. Chem. 2004, 69: 7262

2f Gensini M. de Meijere A. Chem. Eur. J. 2004, 10: 785

2g Kusama H. Miyashita Y. Takaya J. Iwasawa N. Org. Lett. 2006, 8: 289

2h Wilson RM. Thalji RK. Bergman RG. Ellman JA. Org. Lett. 2006, 8: 1745

2i Abbiati G. Casoni A. Canevari V. Nava D. Rossi E. Org. Lett. 2006, 8: 4839

2j Johansen MB. Kerr MA. Org. Lett. 2008, 10: 3497

For reviews on mitomycins, see:

3a Rajski SR. Williams RM. Chem. Rev. 1998, 98: 2723

3b Wolkenberg SE. Boger DL. Chem. Rev. 2002, 102: 2477

3c Galm U. Hager MH. Van Lanen SG. Ju J. Thorson JS. Shen B. Chem. Rev. 2005, 105: 739

3d Wilson RM. Danishefsky SJ. Chem. Soc. Rev. 2007, 36: 1207

For recent reviews on organocatalysis, see:

4a Berkessel A. Gröger H. Asymmetric Organocatalysis Wiley-VCH; Weinheim: 2005.

4b Dalko PI. Enantioselective Organocatalysis Wiley-VCH; Weinheim: 2007.

4c Special issue on organocatalysis: Chem. Rev. 2007, 107: 5413-5883

4d Pellissier H. Tetrahedron 2007, 63: 9267

4e de Figueiredo R. M. Christmann M. Eur. J. Org. Chem. 2007, 2575

4f Dondoni A. Massi A. Angew. Chem. Int. Ed. 2008, 47: 4638 ; Angew. Chem. 2008, 120, 4716

4g Kotsuki H. Ikishima H. Okuyama A. Heterocycles 2008, 75: 493

4h Kotsuki H. Ikishima H. Okuyama A. Heterocycles 2008, 75: 757

4i Enders D. Narine AA. J. Org. Chem. 2008, 73: 7857

4j Melchiorre P. Marigo M. Carlone A. Bartoli G. Angew. Chem. Int. Ed. 2008, 47: 6138 ; Angew. Chem. 2008, 120, 6232

4k Bertelsen S. Jørgensen KA. Chem. Soc. Rev. 2009, 38: 2178

4l Bella M. Gasperi T. Synthesis 2009, 1583

For recent reviews on domino reactions, see:

5a Tietze LF. Chem. Rev. 1996, 96: 115

5b Tietze LF. Brasche G. Gericke K. Domino Reactions in Organic Synthesis Wiley-VCH; Weinheim: 2006.

5c Pellissier H. Tetrahedron 2006, 62: 1619

5d Pellissier H. Tetrahedron 2006, 62: 2143

5e Nicolaou KC. Edmonds DJ. Bulger PG. Angew. Chem. Int. Ed. 2006, 45: 7134 ; Angew. Chem. 2006, 118, 7292

5f Chapman CJ. Frost CG. Synthesis 2007, 1

For reviews on organocatalytic domino reactions, see:

6a Enders D. Grondal C. Hüttl MRM. Angew. Chem. Int. Ed. 2007, 46: 1570 ; Angew. Chem. 2007, 119, 1590

6b Yu X. Wang W. Org. Biomol. Chem. 2008, 6: 2037

For selected examples of organocatalytic domino reactions, see:

7a Halland N. Aburel PS. Jørgensen KA. Angew. Chem. Int. Ed. 2004, 43: 1272 ; Angew. Chem. 2004, 116, 1292

7b Yang JW. Fonseca MTH. List B. J. Am. Chem. Soc. 2005, 127: 15036

7c Huang Y. Walji AM. Larsen CH. MacMillan DWC. J. Am. Chem. Soc. 2005, 127: 15051

7d Marigo M. Schulte T. Franzén J. Jørgensen KA. J. Am. Chem. Soc. 2005, 127: 15710

7e Enders D. Hüttl MRM. Grondal C. Raabe G. Nature 2006, 441: 861

7f Wang W. Li H. Wang J. Zu L. J. Am. Chem. Soc. 2006, 128: 10354

7g Enders D. Hüttl MRM. Runsink J. Raabe G. Wendt B. Angew. Chem. Int. Ed. 2007, 46: 467 ; Angew. Chem. 2007, 119, 471

7h Enders D. Narine AA. Benninghaus TR. Raabe G. Synlett 2007, 1667

7i Carlone A. Cabrera S. Marigo M. Jørgensen KA. Angew. Chem. Int. Ed. 2007, 46: 1101 ; Angew. Chem. 2007, 119, 1119

7j Hayashi Y. Okano T. Aratake S. Hazelard D. Angew. Chem. Int. Ed. 2007, 46: 4922 ; Angew. Chem. 2007, 119, 5010

7k Vicario JL. Reboredo L. Badía D. Carrillo L. Angew. Chem. Int. Ed. 2007, 46: 5168 ; Angew. Chem. 2007, 119, 5260

7l Reyes E. Jiang H. Milelli A. Elsner P. Hazell RG. Jørgensen KA. Angew. Chem. Int. Ed. 2007, 46: 9202 ; Angew. Chem. 2007, 119, 9362

7m Xie H. Zu L. Li H. Wang J. Wang W. J. Am. Chem. Soc. 2007, 129: 10886

7n Rueping M. Sugiono E. Merino E. Angew. Chem. Int. Ed. 2008, 47: 3046 ; Angew. Chem. 2008, 120, 3089

7o Enders D. Wang C. Bats JW. Angew. Chem. Int. Ed. 2008, 47: 7539 ; Angew. Chem. 2008, 120, 7649

7p Zhao G.-L. Rios R. Vesley J. Eriksson L. Córdova A. Angew. Chem. Int. Ed. 2008, 47: 8468 ; Angew. Chem. 2008, 120, 8596

7q Lu M. Zhu D. Lu Y. Hou Y. Tan B. Zhong G. Angew. Chem. Int. Ed. 2008, 47: 10187 ; Angew. Chem. 2008, 120, 10341

7r Enders D. Hüttl MRM. Raabe G. Bats JW. Adv. Synth. Catal. 2008, 350: 267

7s Kotame P. Hong B.-C. Liao J.-H. Tetrahedron Lett. 2009, 50: 704

7t Enders D. Wang C. Bats JW. Synlett 2009, 1777

7u Reyes E. Talavera G. Vicario JL. Badía D. Carrillo L. Angew. Chem. Int. Ed. 2009, 48: 5701 ; Angew. Chem. 2009, 121, 5811

7v Bencivenni G. Wu L.-Y. Mazzanti A. Giannichi B. Pesciaioli F. Song M.-P. Bartoli G. Melchiorre P. Angew. Chem. Int. Ed. 2009, 48: 7200 ; Angew. Chem. 2009, 121, 7336

For reviews on 1,4-addition reactions catalyzed by organocatalysts, see:

8a Tsogoeva SB. Eur. J. Org. Chem. 2007, 1701

8b Sulzer-Mossé S. Alexakis A. Chem. Commun. 2007, 3123

8c Vicario JL. Badía D. Carrillo L. Synthesis 2007, 2065

8d Almaºi D. Alonso DA. Nájera C. Tetrahedron: Asymmetry 2007, 18: 299

For selected examples of organocatalytic aza-Michael additions, see:

9a Guerin DJ. Miller SJ. J. Am. Chem. Soc. 2002, 124: 2134

9b Yamamoto Y. Momiyama N. Yamamoto H. J. Am. Chem. Soc. 2004, 126: 5962

9c Chen YK. Yoshida M. MacMillan DWC. J. Am. Chem. Soc. 2006, 128: 9328

9d Wang J. Li H. Zu L. Wang W. Org. Lett. 2006, 8: 1391

9e Vesely J. Ibrahem I. Zhao G.-L. Rios R. Córdova A. Angew. Chem. Int. Ed. 2007, 46: 778 ; Angew. Chem. 2007, 119, 792

9f Uria U. Vicario JL. Badía D. Carrillo L. Chem. Commun. 2007, 2509

9g Dinér P. Nielsen M. Marigo M. Eriksson L. Jørgensen KA. Angew. Chem. Int. Ed. 2007, 46: 1983 , Angew. Chem. 2007, 119, 2029

9h Li H. Wang J. Xie H. Zu L. Jiang W. Duesler EN. Wang W. Org. Lett. 2007, 9: 965

9i Fustero S. Jiménez D. Moscardó J. Catalán S. del Pozo C. Org. Lett. 2007, 9: 5283

9j Sibi MP. Itoh K. J. Am. Chem. Soc. 2007, 129: 8064

9k Bandini M. Eichholzer A. Tragni M. Umani-Ronchi A. Angew. Chem. Int. Ed. 2008, 47: 3238 ; Angew. Chem. 2008, 120, 3282

9l Enders D. Narine AA. Toulgoat F. Bisshops T. Angew. Chem. Int. Ed. 2008, 47: 5661 ; Angew. Chem. 2008, 120, 5744

9m Lu X. Deng L. Angew. Chem. Int. Ed. 2008, 47: 7710 ; Angew. Chem. 2008, 120, 7824

9n Tan B. Shi Z. Chua PJ. Li Y. Zhong G. Angew. Chem. Int. Ed. 2009, 48: 758 ; Angew. Chem. 2009, 121, 772

9o Uraguchi D. Nakashima D. Ooi T. J. Am. Chem. Soc. 2009, 131: 7242

For the first applications of diphenylprolinol TMS-ether, see:

10a Marigo M. Wabnitz TC. Fielenbach D. Jørgensen KA. Angew. Chem. Int. Ed. 2005, 44: 794 ; Angew. Chem. 2005, 117, 804

10b Hayashi Y. Gotoh H. Hayashi T. Shoji M. Angew. Chem. Int. Ed. 2005, 44: 4212 ; Angew. Chem. 2005, 117, 4284

For reviews on diphenylprolinol TMS-ether catalysis, see:

11a Palomo C. Mielgo A. Angew. Chem. Int. Ed. 2006, 45: 7876 ; Angew. Chem. 2006, 118, 8042

11b Mielgo A. Palomo C. Chem. Asian J. 2008, 922

12

CCDC-737780 contains the supplementary crystallographic data for the compound 3b reported in this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.