N-Arylation of Sterically Hindered NH-Nucleophiles: Copper-Mediated­ Syntheses of Diverse N-Arylindole-2-carboxylates

Jinyong Lee; Ji Hye Choi; Seunghoon Shin; Jung-Nyoung Heo; Hwan Jung Lim

doi:10.1055/s-0035-1560065

Synthesis, Table of Contents

Synthesis 2015; 47(21): 3301-3308
DOI: 10.1055/s-0035-1560065

paper

N-Arylation of Sterically Hindered NH-Nucleophiles: Copper-Mediated Syntheses of Diverse N-Arylindole-2-carboxylates

Jinyong Lee

^aMedicinal Chemistry Research Center, Korea Research Institute of Chemical Technology, 141 Gajeong-ro, Daejeon 305-345, Republic of Korea Email: indium@krict.re.kr

^cGraduate School of New Drug Discovery & Development Chungnam National University, Daejeon 305-764, Republic of Korea

,

Ji Hye Choi

^aMedicinal Chemistry Research Center, Korea Research Institute of Chemical Technology, 141 Gajeong-ro, Daejeon 305-345, Republic of Korea Email: indium@krict.re.kr

^bDepartment of Chemistry, Hanyang University Seoul, 133-791, Republic of Korea

,

Seunghoon Shin

^bDepartment of Chemistry, Hanyang University Seoul, 133-791, Republic of Korea

,

Jung-Nyoung Heo

^aMedicinal Chemistry Research Center, Korea Research Institute of Chemical Technology, 141 Gajeong-ro, Daejeon 305-345, Republic of Korea Email: indium@krict.re.kr

^cGraduate School of New Drug Discovery & Development Chungnam National University, Daejeon 305-764, Republic of Korea

,

Hwan Jung Lim*

^aMedicinal Chemistry Research Center, Korea Research Institute of Chemical Technology, 141 Gajeong-ro, Daejeon 305-345, Republic of Korea Email: indium@krict.re.kr

^dDepartment of Medicinal and Pharmaceutical Chemistry, University of Science & Technology, 217 Gajeong-ro, Daejeon 305-350, Republic of Korea

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Abstract

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Abstract

Indole-carboxylates are N-arylated with 2-bromopyridines using stoichiometric copper(II) oxide/potassium carbonate to give various N-(2-pyridyl)-substituted indole-2-carboxylates and with bromobenzenes using stoichiometric copper(I) iodide/N,N′-dimethylethylenediamine to give various N-(substituted phenyl)-substituted indole-2-carboxylates. These results expand the scope of metal-catalyzed N-arylation using heterocyclic amines with steric bulk and weak nucleophilicity.

Key words

copper - N-arylation - indoles - copper-mediated synthesis - heterocyclic amines - metal-catalyzed

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References

References

1a Comprehensive Heterocyclic Chemistry II . Katritzky AR, Rees CW, Scriven EF. V. Elsevier; Oxford: 1996
1b Craig PN In Comprehensive Medicinal Chemistry . Vol. 8. Drayton CJ. Pergamon; Oxford: 1991
1c Cozzi P, Carganico G, Fusar D, Grossoni M, Menichincheri M, Pinciroli V, Tonani R, Vaghi F, Salvati P. J. Med. Chem. 1993; 36: 2964

2a Pelcman B, Olofsson K, Katkevics M, Ozola V, Suna E, Kalvins I, Trapencieris P, Katkevica D, Schaal W. WO 2006077367, 2006
2b Dubois L, Evanno Y, Malanda A, Maloizel C. WO 2008107544, 2008
2c Sinz C, Bittner A, Brady E, Candelore M, Dallas-Yang Q, Ding V, Jiang G, Lin Z, Qureshi S, Salituro G, Saperstein R, Shang J, Szalkowski D, Tota L, Vincent S, Wright M, Xu S, Yang X, Zhang B, Tata J, Kim R, Parmee ER. Bioorg. Med. Chem. Lett. 2011; 21: 7124
2d Olofsson K, Suna E, Pelcman B, Ozola V, Katkevics M, Kalvins I, Schaal W. WO 2005123675, 2005

For reviews of metal-catalyzed N-arylation of indoles, see

3a Djakovitch L, Batail N, Genelot M. Molecules 2011; 16: 5241 ; http://www.mdpi.com/journal/molecules
3b Xu H. Mini-Rev. Org. Chem. 2009; 6: 367
3c Monnier F, Taillefer M. Angew. Chem. Int. Ed. 2009; 48: 6954

4a Klapars A, Antilla JC, Huang X, Buchwald SL. J. Am. Chem. Soc. 2001; 123: 7727
4b Antilla JC, Klapars A, Buchwald SL. J. Am. Chem. Soc. 2002; 124: 11684
4c Altman RA, Koval ED, Buchwald SL. J. Org. Chem. 2007; 72: 6190
4d Zhu L, Cheng L, Zhang Y, Xie R, You J. J. Org. Chem. 2007; 72: 2737
4e Correa A, Bolm C. Angew. Chem. Int. Ed. 2007; 46: 8862
4f Rao RK, Naidu AB, Jaseer EA, Sekar G. Tetrahedron 2009; 65: 4619
4g Verma AK, Singh J, Larock RC. Tetrahedron 2009; 65: 8434
4h Zhu L, Li G, Luo L, Guo P, Lan J, You J. J. Org. Chem. 2009; 74: 2200
4i Sreedhar B, Shiva Kumar KB, Srinivas P, Balasubrahmanyam V, Venkanna GT. J. Mol. Catal. A: Chem. 2007; 265: 183
4j Yang X, Xing H, Zhang Y, Lai Y, Zhang Y, Jiang Y, Ma D. Chin. J. Chem. 2012; 30: 875
4k Liu S, Zhou J. New J. Chem. 2013; 37: 2537
4l Larsson P.-F, Correa A, Carril M, Norrby P.-O, Bolm C. Angew. Chem. Int. Ed. 2009; 48: 5691
4m Swapna K, Murthy SN, Nageswar YV. D. Eur. J. Org. Chem. 2010; 6678

5a Barton DH. R, Finet J.-P, Khamsi J. Tetrahedron Lett. 1988; 29: 1115
5b Barton DH. R, Finet J.-P, Khamsi J. Tetrahedron Lett. 1986; 27: 3615

6 Beach MJ, Hope R, Klaubert DH, Russell RK. Synth. Commun. 1995; 25: 2165
7 Mederski WW. K. R, Lefort M, Germann M, Kux D. Tetrahedron 1999; 55: 12757
8 Beletskaya IP, Cheprakov AV. Organometallics 2012; 31: 7753

9a Ishii H, Sugiura T, Akiyama Y, Ichikawa Y, Watanabe T, Murakami Y. Chem. Pharm. Bull. 1990; 38: 2118
9b Ishii H, Takeda H, Hagiwara T, Sakamoto M, Kogusuri K. J. Chem. Soc., Perkin Trans. 1 1989; 2407

10a Brown JA. Tetrahedron Lett. 2000; 41: 1623
10b Yamazaki K, Nakamura Y, Kondo Y. J. Org. Chem. 2003; 68: 6011
10c Vieira TO, Meaney LA, Shi Y.-L, Alper H. Org. Lett. 2008; 10: 4899

For reviews and selected reports, see:

11a Ley SV, Thomas AW. Angew. Chem. Int. Ed. 2003; 42: 5400
11b Lindley J. Tetrahedron 1984; 40: 1433
11c Kunz K, Scholz U, Ganzer D. Synlett 2003; 2428
11d Beletskaya IP, Cheprakov AV. Coord. Chem. Rev. 2004; 248: 2337
11e Corbet J.-P, Mignani G. Chem. Rev. 2006; 106: 2651
11f Ma D, Zhang Y, Yao J, Wu S, Tao F. J. Am. Chem. Soc. 1998; 120: 12459
11g Yamada K, Kurokawa T, Tokuyama H, Fukuyama T. J. Am. Chem. Soc. 2003; 125: 6630

12 Wang R, Shi H.-F, Zhao J.-F, He Y.-P, Zhang H.-B, Liu J.-P. Bioorg. Med. Chem. Lett. 2013; 23: 1760
13 Choi JH, Lim HJ. Org. Biomol. Chem. 2015; 13: 5131
14 Kim H.-Y, Yoon J.-Y, Yun J.-H, Cho K.-W, Lee S.-H, Rhee Y.-M, Jung H.-S, Lim HJ, Lee H, Choi J, Heo J.-N, Lee W, No K.-T, Min D, Choi K.-Y. Cell Death Differ. 2015; 22: 912

Supplementary Material

Supporting Information

N-Arylation of Sterically Hindered NH-Nucleophiles: Copper-Mediated­ Syntheses of Diverse N-Arylindole-2-carboxylates

N-Arylation of Sterically Hindered NH-Nucleophiles: Copper-Mediated Syntheses of Diverse N-Arylindole-2-carboxylates