Copper-Catalyzed C–N Bond Formation with N-Heterocycles and Aryl 
Halides

Mikki G. Boswell; Fanny G. Yeung; Christian Wolf

doi:10.1055/s-0031-1290827

Synlett, Table of Contents

Synlett 2012; 23(8): 1240-1244
DOI: 10.1055/s-0031-1290827

letter

Copper-Catalyzed C–N Bond Formation with N-Heterocycles and Aryl Halides

Mikki G. Boswell

Department of Chemistry, Georgetown University, Washington, DC 20057, USA, Fax: +1(202)6876209 Email: cw27@georgetown.edu

,

Fanny G. Yeung

Department of Chemistry, Georgetown University, Washington, DC 20057, USA, Fax: +1(202)6876209 Email: cw27@georgetown.edu

,

Christian Wolf*

Department of Chemistry, Georgetown University, Washington, DC 20057, USA, Fax: +1(202)6876209 Email: cw27@georgetown.edu

› Author Affiliations

Abstract

All articles of this category

Abstract

The microwave-assisted, cuprous oxide catalyzed coupling of aryl bromides and iodides with imidazole, benzimidazole, pyrazole, or triazole was found to give a wide range of N-aryl heteroaromatic products in good to high yields. Aryl dibromides undergo selective monosubstitution even in the presence of large excess of N-heterocyclic nucleophiles which leaves the second aryl bromide functionality intact for further derivatization.

Key words

copper - cross-coupling - N-heterocycles - aryl halides - microwave

Full Text

References

References and Notes
1 Monnier F, Taillefer M. Angew. Chem. Int. Ed. 2009; 48: 6954

Selected examples of Pd catalysis:
2a Hartwig JF, Kawatsura M, Hauck SI, Shaughnessy KH, Alcazar-Roman LM. J. Org. Chem. 1999; 64: 5575
2b Wolfe JP, Tomori H, Sadighi JP, Yin J, Buchwald SL. J. Org. Chem. 2000; 65: 1158
2c Poondra RR, Turner NJ. Org. Lett. 2005; 7: 863
2d Shen Q, Shecar S, Stambuli JP, Hartwig JF. Angew. Chem. Int. Ed. 2005; 44: 1371
2e Hagopian LE, Campbell AN, Golen JA, Rheingold AL, Nataro C. J. Organomet. Chem. 2006; 691: 4890
2f Xie X, Zhang TY, Zhang Z. J. Org. Chem. 2006; 71: 6522
2g Trabanco AA, Vega JA, Fernandez MA. J. Org. Chem. 2007; 72: 8146
2h Biscoe MR, Fors BP, Buchwald SL. J. Am. Chem. Soc. 2008; 130: 6686
2i Fors BP, Krattiger P, Strieter E, Buchwald SL. Org. Lett. 2008; 10: 3505
2j Shen Q, Hartwig JF. Org. Lett. 2008; 10: 4109
2k Surry DS, Buchwald SL. Angew. Chem. Int. Ed. 2008; 47: 6338
2l Ogata T, Hartwig JF. J. Am. Chem. Soc. 2008; 130: 13848
2m Fors BP, Watson DA, Biscoe MR, Buchwald SL. J. Am. Chem. Soc. 2008; 130: 13552
2n Shen Q, Ogata T, Hartwig JF. J. Am. Chem. Soc. 2008; 130: 6586
2o Vo GD, Hartwig JF. J. Am. Chem. Soc. 2009; 131: 11049
2p Maiti D, Buchwald SL. J. Am. Chem. Soc. 2009; 131: 17423
2q Lundgren RJ, Sappong-Kumankumah A, Stradiotto M. Chem. Eur. J. 2010; 16: 1983
2r Koley M, Schnuerch M, Mihovilovic MD. Synlett 2010; 1505
2s Johansson Seechurn CC. C, Parisel SL, Colacot TJ. J. Org. Chem. 2011; 76: 7918
2t Chartoire A, Lesieur M, Slawin AM. Z, Nolan SP, Cazin CS. J. Organometallics 2011; 30: 4432

Selected examples of Cu catalysis:
3a Ma D, Zhang Y, Yao J, Wu S, Tao F. J. Am. Chem. Soc. 1998; 120: 12459
3b Kwong FY, Klapars A, Buchwald SL. Org. Lett. 2002; 4: 581
3c Antilla JC, Klapars A, Buchwald SL. J. Am. Chem. Soc. 2002; 124: 11684
3d Ma D, Cai Q, Zhang H. Org. Lett. 2003; 5: 2453
3e Cristeau H.-J, Cellier PP, Spindler J.-F, Taillefer M. Chem. Eur. J. 2004; 10: 5607
3f Mei X, Wolf C. J. Org. Chem. 2005; 70: 2299
3g Lu Z, Twieg RJ. Tetrahedron Lett. 2005; 46: 2997
3h Zhang H, Cai Q, Ma D. J. Org. Chem. 2005; 70: 5164
3i Rao H, Fu H, Jiang Y, Zhao Y. J. Org. Chem. 2005; 70: 8107
3j Guo X, Rao H, Fu H, Jiang Y, Zhao Y. Adv. Synth. Catal. 2006; 348: 2197
3k Mei X, August AT, Wolf C. J. Org. Chem. 2006; 71: 142
3l Wolf C, Liu S, Mei X, August AT, Casimir MD. J. Org. Chem. 2006; 71: 3270
3m De Lange B, Lambers-Verstappen MH, Schmieder-van de Vondovoroort L, Sereinig N, de Rijk R, de Vries AH. M, de Vries JG. Synlett 2006; 3105
3n Zhu X, Ma Y, Su L, Song H, Chen G, Liang D, Wan Y. Synthesis 2006; 3955
3o Shafir A, Buchwald SL. J. Am. Chem. Soc. 2006; 128: 8742
3p Liu S, Pestano JP. C, Wolf C. Synthesis 2007; 3519
3q Altman RA, Koval ED, Buchwald SL. J. Org. Chem. 2007; 72: 6190
3r Rout L, Jammi S, Punniyamurthy T. Org. Lett. 2007; 9: 3397
3s Altman RA, Shafir A, Choi A, Lichtor PA, Buchwald SL. J. Org. Chem. 2008; 73: 284
3t Altman RA, Anderson KW, Buchwald SL. J. Org. Chem. 2008; 73: 5167
3u Xia N, Taillefer M. Angew. Chem. Int. Ed. 2009; 48: 337
3v Jiang L, Lu X, Zhang H, Jiang Y, Ma D. J. Org. Chem. 2009; 74: 4542
3w Wu X.-F, Darcel C. Eur. J. Org. Chem. 2009; 4753
3x Liu X, Zhang S. Synlett 2011; 1137

4a Hartwig JF, Kawatsura M, Hauck SI, Shaughnessy KH, Alcazar-Roman LM. J. Org. Chem. 1999; 64: 5575
4b Yin J, Buchwald SL. Org. Lett. 2000; 2: 1101
4c Yin J, Buchwald SL. J. Am. Chem. Soc. 2002; 124: 6043
4d Huang X, Anderson KW, Zim D, Jiang L, Klapars A, Buchwald SL. J. Am. Chem. Soc. 2003; 125: 6653
4e Shi F, Smith MR. III, Maleczka RE. Jr. Org. Lett. 2006; 8: 1411
4f Shen Q, Hartwig JF. J. Am. Chem. Soc. 2007; 129: 7734
4g Ikawa T, Barder TE, Biscoe MR, Buchwald SL. J. Am. Chem. Soc. 2007; 129: 13001
4h Fors BP, Krattiger P, Strieter E, Buchwald SL. Org. Lett. 2008; 10: 3505
4i Strieter ER, Bhayana B, Buchwald SL. J. Am. Chem. Soc. 2009; 131: 78
4j Fors BP, Dooleweerdt K, Zeng Q, Buchwald SL. Tetrahedron 2009; 65: 6576
4k Dooleweerdt K, Fors BP, Buchwald SL. Org. Lett. 2010; 12: 2350
4l Hicks JD, Hyde AM, Martinez Cuezva A, Buchwald SL. J. Am. Chem. Soc. 2009; 131: 16720

5 McLaughlin M, Palucki M, Davies IW. Org. Lett. 2006; 8: 3311
6 Ghosh A, Sieser JE, Riou M, Cai W, Rivera-Ruiz L. Org. Lett. 2003; 5: 2207
7 Manley PJ, Bilodeau MT. Org. Lett. 2004; 6: 2433

8a Klapars A, Huang X, Buchwald SL. J. Am. Chem. Soc. 2002; 124: 7421
8b Jiang L, Job GE, Klapars A, Buchwald SL. Org. Lett. 2003; 5: 3667
8c Hosseinzadeh R, Tajbaksh M, Mohadjerani M, Mehdinejad H. Synlett 2004; 1517
8d Deng W, Wang Y.-F, Zou Y, Liu L, Guo Q.-X. Tetrahedron Lett. 2004; 45: 2311
8e Klapars A, Parris S, Anderson KW, Buchwald SL. J. Am. Chem. Soc. 2004; 126: 3529
8f Strieter ER, Blackmond DG, Buchwald SL. J. Am. Chem. Soc. 2005; 127: 4120
8g Moriwaki K, Satoh K, Takada M, Ishino Y, Ohno T. Tetrahedron Lett. 2005; 46: 7559
8h Chandrasekhar S, Sultana SS, Yaragorla SR, Reddy NR. Synthesis 2006; 839
8i Yadav LD. S, Yadav BS, Rai VK. Synthesis 2006; 1868
8j Tye JW, Weng Z, Johns AM, Incarvito CD, Hartwig JF. J. Am. Chem. Soc. 2008; 130: 9971
8k Strieter ER, Bhayana B, Buchwald SL. J. Am. Chem. Soc. 2009; 131: 78

9a Correa A, Bolm C. Adv. Synth. Catal. 2007; 349: 2673
9b Chow WS, Chan TH. Tetrahedron Lett. 2009; 50: 1286
9c Zhu L, Li G, Luo L, Guo P, Lan JYou J. J. Org. Chem. 2009; 74: 2200
9d Chen H, Wang D, Wang X, Huang W, Cai Q, Ding K. Synthesis 2010; 1505
9e Xu Z.-L, Li H.-X, Ren Z.-G, Du W.-Y, Xu W.-C, Lang J.-P. Tetrahedron 2011; 67: 5282

10a Xu H, Wolf C. Chem. Commun. 2009; 1715
10b Xu H, Wolf C. Chem. Commun. 2009; 3035

11 This amination protocol has been successfully incorporated into an advanced undergraduate laboratory course
12 The selective monoamination of 2,6-dibromopyridine with amines has been reported: Bolliger JL, Oberholzer M, Frech CM. Adv. Synth. Catal. 2011; 353: 945
13 This procedure gave unsatisfactory results when pyrrole and indole were used

14a Lam PY. S, Clark CG, Saubern S, Adams J, Winters MP, Chan DM. T, Combs A. Tetrahedron Lett. 1998; 39: 2941
14b Sreedhar B, Venkanna GT, Kumar KB. S, Balassubrahmanyam V. Synthesis 2008; 795

15 Garfinkel D, Edsall JT. J. Am. Chem. Soc. 1958; 80: 3807

Supplementary Material

Supporting Information