Tandem One-Pot Construction
of Indoles via Palladium and Copper-Catalyzed
Coupling Reactions of the Blaise Reaction Intermediate

Ju Hyun Kim; Sang-gi Lee

doi:10.1055/s-0031-1289753

Subscribe to RSS

Please copy the URL and add it into your RSS Feed Reader.

https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000084.xml

Share / Bookmark

Facebook X Linkedin Weibo

Download PDF

Synthesis 2012(10): 1464-1476
DOI: 10.1055/s-0031-1289753

FEATUREARTICLE

Tandem One-Pot Construction of Indoles via Palladium and Copper-Catalyzed Coupling Reactions of the Blaise Reaction Intermediate

Ju Hyun Kim, Sang-gi Lee*
Department of Chemistry and Nano Science (BK21), Ewha Womans University, 120-750 Seoul, Korea
Fax: +82(2)32774505; e-Mail: sanggi@ewha.ac.kr;

Further Information

Publication History

Received 3 January 2012
Publication Date:
29 March 2012 (online)

Abstract
Full Text
References

Permissions and Reprints All articles of this category

Abstract

The palladium-catalyzed intramolecular N-arylation of the Blaise reaction intermediate, formed by reaction of nitriles with an in situ generated Reformatsky reagent from ethyl α-bromo-α-(2-bromophenyl)acetate and zinc, afforded indoles in good yields. Extension of this approach to the chemoselective intramolecular N-alkylation/palladium-catalyzed N-arylation of the Blaise reaction intermediate, having ω-chloroalkyl appendages, provided a novel route for the tandem one-pot synthesis of N-fused indole derivatives. In contrast, the intermolecular coupling reaction of the Blaise reaction intermediates with 1,2-dihalobenzene did not proceed in the presence of a palladium catalyst, but proceeded in the presence of copper(I) iodide as the catalyst and resulted in indoles.

1 Introduction

2 Results and Discussion

2.1 Palladium-Catalyzed Intramolecular C-N Coupling Reaction of the Blaise Reaction Intermediate

2.2 Chemoselective Intramolecular N-Alkylation/Palladium-Catalyzed C-N Coupling Reaction of the Blaise Reaction Intermediate

2.3 Copper-Catalyzed Intermolecular N-C/C-C Coupling Reaction of the Blaise Reaction Intermediate with 1,2-Dihaloarenes

3 Conclusion

Key words

tandem reaction - Blaise reaction - palladium - copper - coupling - indoles

References

1a Evans BE. Rittle KE. Bock MG. Dipardo RM. Freidinger RM. Whitter WL. Lundell GF. Veber DF. Anderson PS. J. Med. Chem. 1988, 31: 2235

Google Scholar
1b Nicolaou KC. Pfefferkorn JA. Roecker AJ. Cao G.-Q. Barluenga S. Mitchell HJ. J. Am. Chem. Soc. 2000, 122: 9939

Google Scholar
1c Kleeman A. Engel J. Kutscher B. Reichert D. Pharmaceutical Substances 4th ed.: Thieme; New York: 2001.

Google Scholar
1d Humphrey GR. Kuethe JT. Chem. Rev. 2006, 106: 2875

Google Scholar
For some recent reviews for indole synthesis, see:
2a Sundberg RJ. Indoles Academic Press; San Diego: 1996.

Google Scholar
2b Gribble GW. J. Chem. Soc., Perkin Trans. 1 2000, 1045

Google Scholar
2c Gilchrist TL. J. Chem. Soc., Perkin Trans. 1 2001, 2491

Google Scholar
2d Joule JA. In Science of Synthesis Vol. 10: Thomas EJ. Thieme; Stuttgart: 2000. p.361

Google Scholar
For selected recent examples of indole synthesis, see:
3a Takeda A. Kamijo S. Yamamoto Y. J. Am. Chem. Soc. 2000, 122: 5662

Google Scholar
3b Rutherford JL. Rainka MP. Buchwald SL. J. Am. Chem. Soc. 2002, 124: 15168

Google Scholar
3c Siebeneicher H. Bytschkov I. Doye S. Angew. Chem. Int. Ed. 2003, 42: 3042

Google Scholar
3d Taber DF. Tian W. J. Am. Chem. Soc. 2006, 128: 1058

Google Scholar
3e Ackermann L. Synlett 2007, 507

Google Scholar
3f Ohno H. Ohta Y. Oishi S. Fujii N. Angew. Chem. Int. Ed. 2007, 46: 2295

Google Scholar
3g Cariou K. Ronan B. Mignani S. Fensterbank L. Malacria M. Angew. Chem. Int. Ed. 2007, 46: 1881

Google Scholar
3h Alex K. Tillack A. Schwarz N. Beller M. Angew. Chem. Int. Ed. 2008, 47: 2304

Google Scholar
3i Kraus GA. Guo H. Org. Lett. 2008, 10: 3061

Google Scholar
3j El Kaim L. Gizzi M. Grimaud L. Org. Lett. 2008, 10: 3417

Google Scholar
3k Cui S.-L. Wang J. Wang Y.-G. J. Am. Chem. Soc. 2008, 130: 13526

Google Scholar
For some recent reviews on Pd-catalyzed indole synthesis, see:
4a Li JJ. Gribble GW. Palladium in Heterocyclic Chemistry Pergamon; Oxford: 2000.

Google Scholar
4b Cacchi S. Fabrizi G. Chem. Rev. 2005, 105: 2873

Google Scholar
5a Larock RC. Yum EK. J. Am. Chem. Soc. 1991, 113: 6689

Google Scholar
5b Larock RC. Yum EK. Refvik MD. J. Org. Chem. 1998, 63: 7652

Google Scholar
5c Shen M. Li G. Lu BZ. Hossain A. Roschangar F. Farina V. Senanayake CH. Org. Lett. 2004, 6: 4129

Google Scholar
6a Stuart DR. Bertrand-Laperle M. Burgess KMN. Fagnou K. J. Am. Chem. Soc. 2008, 130: 16474

Google Scholar
For a similar result for the Pd(II)-catalyzed preparation of indoline using a urea moiety as the activating group, see:
6b Houlden CE. Bailey CD. Ford JG. Gagné MR. Lloyd-Jones GC. Booker-Milburn KI. J. Am. Chem. Soc. 2008, 130: 10066

Google Scholar
6c Shi Z. Zhang C. Li S. Pan D. Ding S. Cui Y. Jiao N. Angew. Chem. Int. Ed. 2009, 48: 4572

Google Scholar
7a Thielges S. Meddah E. Bisseret P. Eustache J. Tetrahedron Lett. 2004, 45: 907

Google Scholar
7b Fang Y.-Q. Lautens M. Org. Lett. 2005, 7: 3549

Google Scholar
7c Fayol A. Fang Y.-Q. Lautens M. Org. Lett. 2006, 8: 4203

Google Scholar
7d Fang Y.-Q. Lautens M. J. Org. Chem. 2008, 73: 538

Google Scholar
7e Newman SG. Lautens M. J. Am. Chem. Soc. 2010, 132: 11416

Google Scholar
8a Willis MC. Brace GN. Holmes IP. Angew. Chem. Int. Ed. 2005, 44: 403

Google Scholar
8b Fletcher AJ. Bax MN. Willis MC. Chem. Commun. 2007, 4764

Google Scholar
9a Barluenga J. Jiménez-Aquino A. Valdés C. Aznar F. Angew. Chem. Int. Ed. 2007, 46: 1529

Google Scholar
9b Barluenga J. Jiménez-Aquino A. Aznar F. Valdés C. J. Am. Chem. Soc. 2009, 131: 4031

Google Scholar
10 Wrütz S. Rakshit S. Neumann JJ. Dröge T. Glorius F. Angew. Chem. Int. Ed. 2008, 47: 7230

Google Scholar
11a Battistuzzi G. Cacchi S. Fabrizi G. Eur. J. Org. Chem. 2002, 2671

Google Scholar
11b Cacchi S. Fabrizi G. Parisi LM. Synthesis 2004, 1889

Google Scholar
12a Ho T.-L. Tandem Organic Reactions Wiley; New York: 1992.

Google Scholar
12b Tietze LF. Brasche G. Gericke KM. Domino Reactions in Organic Synthesis Wiley-VCH; Weinheim: 2006.

Google Scholar
12c Nicolaou KC. Edmonds DJ. Bulger PG. Angew. Chem. Int. Ed. 2006, 45: 7134

Google Scholar
12d Fürstner A. Angew. Chem. Int. Ed. 2009, 48: 1364

Google Scholar
12e Parsons PJ. Penkett CS. Shell AJ. Chem. Rev. 1996, 96: 195

Google Scholar
13a Feringa BL. Pineschi M. Arnold LA. Imbos R. de Vries AHM. Angew. Chem. Int. Ed. 1997, 36: 2620

Google Scholar
13b Alexakis A. Trevitt GP. Bernardinelli G. J. Am. Chem. Soc. 2001, 123: 4358

Google Scholar
13c Mizutani H. Degrado SJ. Hoveyda AH. J. Am. Chem. Soc. 2002, 124: 779

Google Scholar
13d Agapiou K. Cauble DF. Krische MJ. J. Am. Chem. Soc. 2004, 126: 4528

Google Scholar
13e Greszler SN. Johnson JS. Angew. Chem. Int. Ed. 2009, 48: 3689

Google Scholar
13f Greszler SN. Malinowski JT. Johnson JS. J. Am. Chem. Soc. 2010, 132: 17393

Google Scholar
14a Haag BA. Zhang Z.-G. Li J.-S. Knochel P. Angew. Chem. Int. Ed. 2010, 49: 9513

Google Scholar
14b Zhang Z.-G. Haag BA. Li J.-S. Knochel P. Synthesis 2011, 23

Google Scholar
15a Blaise EE. C. R. Hebd. Seances Acad. Sci. 1901, 132: 478

Google Scholar
15b Blaise EE. C. R. Hebd. Seances Acad. Sci. 1901, 132: 987

Google Scholar
15c Rathke MW. Weipert P. Zinc Enolates: The Reformatsky and Blaise Reaction, In Comprehensive Organic Reactions Vol. 2: Trost BM. Pergamon; Oxford: 1991. p.277-299

Google Scholar
15d Rao HSP. Rafi S. Padmavathy K. Tetrahedron 2008, 64: 8037

Google Scholar
16a Chun YS. Lee KK. Ko YO. Shin H. Lee S.-g. Chem. Commun. 2008, 5098

Google Scholar
16b Ko YO. Chun YS. Park C.-L. Kim Y. Shin H. Ahn S. Hong J. Lee S.-g. Org. Biomol. Chem. 2009, 7: 1132

Google Scholar
16c Chun YS. Ko YO. Shin H. Lee S.-g. Org. Lett. 2009, 11: 3414

Google Scholar
16d Chun YS. Ryu KY. Ko YO. Hong JY. Hong J. Shin H. Lee S.-g. J. Org. Chem. 2009, 74: 7556

Google Scholar
16e Ko YO. Chun YS. Kim Y. Kim SJ. Shin H. Lee S.-g. Tetrahedron Lett. 2010, 51: 6893

Google Scholar
16f Chun YS. Ryu KY. Kim JH. Shin H. Lee S.-g. Org. Biomol. Chem. 2011, 9: 1317

Google Scholar
16g Chun YS. Lee JH. Kim JH. Ko YO. Lee S.-g. Org. Lett. 2011, 13: 6390

Google Scholar
17a Jiang L. Buchwald SL. Metal-Catalyzed Cross Coupling Reactions 2nd ed., Vol. 2: Wiley-VCH; Weinheim: 2004. p.699-760

Google Scholar
17b Muci AR. Buchwald SL. Top. Curr. Chem. 2002, 219: 131

Google Scholar
17c Hartwig JF. In Handbook of Organopalladium Chemistry for Organic Synthesis Vol. 1: Wiley-Interscience; New York: 2002. p.1051-1096

Google Scholar
17d Schlummer B. Scholz U. Adv. Synth. Catal. 2004, 346: 1599

Google Scholar
17e Nakamura I. Yamamoto Y. Chem. Rev. 2004, 104: 2127

Google Scholar
18 Kim JH. Lee S.-g. Org. Lett. 2011, 13: 1350

Google Scholar
19a Shelby Q. Kataoka N. Mann G. Hartwig J. J. Am. Chem. Soc. 2000, 122: 10718

Google Scholar
19b Hama T. Culkin DA. Hartwig JF. J. Am. Chem. Soc. 2006, 128: 4976

Google Scholar
20 Barder TE. Walker SD. Martinelli JR. Buchwald SL. J. Am. Chem. Soc. 2005, 127: 4685

Google Scholar
21 Huang X. Anderson KW. Zim D. Jian L. Klapars A. Buchwald SL. J. Am. Chem. Soc. 2003, 125: 6653

Google Scholar
22 Feringa BL. Acc. Chem. Res. 2000, 33: 346

Google Scholar
23 Kitamura M. Tokunaga M. Ohkuma T. Noyori R. Org. Synth. Coll. Vol. IX John Wiley & Sons; London: 1998. p.589

Google Scholar
24 Yin J. Zhao MM. Huffman MA. McNamara JM. Org. Lett. 2002, 4: 3481

Google Scholar
25a Lee S.-g. Zhang YJ. Song CE. Lee JK. Choi JH. Angew. Chem. Int. Ed. 2002, 41: 847

Google Scholar
25b Lee S.-g. Zhang YJ. Org. Lett. 2002, 4: 2429

Google Scholar
25c Zhang YJ. Park JH. Lee S.-g. Tetrahedron: Asymmetry 2004, 15: 2209

Google Scholar
26a Hata T. Sano Y. Sugawara R. Matsumae A. Kanamori K. Shima T. Hoshi T. J. Antibiot. Ser. A 1956, 9: 141

Google Scholar
26b Ewing J. Hughes GK. Ritchie E. Taylor WC. Nature 1952, 169: 618

Google Scholar
26c Yoda N. Hirayama N. J. Med. Chem. 1993, 36: 1461

Google Scholar
26d Goldbrunner M. Loidl G. Polossek T. Mannschreck A. von Angerer E. J. Med. Chem. 1997, 40: 3524

Google Scholar
27a Peters R. Waldmeier P. Joncour A. Org. Process Res. Dev. 2005, 9: 508

Google Scholar
27b Caddick S. Aboutayab K. Jenkins K. West RI. J. Chem. Soc., Perkin Trans. 1 1996, 675

Google Scholar
27c Bennasar M.-L. Roca T. Ferrando F. Org. Lett. 2004, 6: 759

Google Scholar
27d Wang S.-F. Chuang C.-P. Tetrahedron Lett. 1997, 38: 7597

Google Scholar
27e Shiue J.-S. Fang J.-M. J. Chem. Soc., Chem. Commun. 1993, 1277

Google Scholar
27f Ishikura M. Ida W. Yanada K. Tetrahedron 2006, 62: 1015

Google Scholar
27g Verma AK. Kesharwani T. Singh J. Tandon V. Larock RC. Angew. Chem. Int. Ed. 2009, 48: 1138

Google Scholar
27h Fuchibe K. Kaneko T. Mori K. Akiyama T. Angew. Chem. Int. Ed. 2009, 48: 8070

Google Scholar
28 Kim JH. Shin H. Lee S.-g. J. Org. Chem. 2012, 77: 1560

Google Scholar
29 Andrez J.-C. Beilstein J. Org. Chem. 2009, 5 ; DOI: 10.3762/bjoc.5.33

Google Scholar
30a Bernini R. Fabrizi G. Sferrazza A. Cacchi S. Angew. Chem. Int. Ed. 2009, 48: 8078

Google Scholar
30b Moriwaki K. Satoh K. Takada M. Ishino Y. Ohno T. Tetrahedron Lett. 2005, 46: 7559

Google Scholar
31 Sperotto E. Klink GPM. Koten G. Vries JG. Dalton Trans. 2010, 39: 10338

Google Scholar
32 Fotsch C. Bartberger MD. Bercot EA. Chen M. Cupples R. Emery M. Fretland J. Guram A. Hale C. Han N. Hickman D. Hungate RW. Hayashi M. Komorowski R. Liu Q. Matsumoto G. St. Jean DJ. Ursu S. Véniant M. Xu G. Ye Q. Yuan C. Zhang J. Zhang X. Tu H. Wang M. J. Med. Chem. 2008, 51: 7953

Google Scholar
33 Fraley ME. Garbaccio RM. Arrington KL. Hoffman WF. Tasber ES. Coleman PJ. Buser CA. Walsh ES. Hamilton K. Fernandes C. Schaber MD. Lobell RB. Tao W. South VJ. Yan Y. Kuo LC. Prueksaritanont T. Shu C. Torrent M. Heimbrook DC. Kohl NE. Huber HE. Hartman GD. Bioorg. Med. Chem. Lett. 2006, 16: 1775

Google Scholar