Use of Ligand-Free Iron/Copper Cocatalyst for Nitrogen and Sulfur Cross-Coupling Reaction with 6-Iodoimidazo[1,2-a]pyridine

Abstract

A ligand-free cooperative bimetallic iron/copper catalysis system was found to introduce various azoles and thiols onto 6-iodoimidazo[1,2-a] pyridine. After optimization, the inexpensive, nontoxic, air-stable, and commercially available CuO and FeCl₂·4H₂O enabled a regio­selective N- and S-arylation of common nitrogen heterocycles and of a broad range of mercaptans including aliphatic, aromatic, and heterocyclic thiols.

Key words

iron - copper - bimetallic catalysis - imidazo[1,2-a]pyridine - N and S cross-coupling

• References


For latest articles, see:
• 1a Miller JF, Chong PK, Shotwell JB, Catalano JG, Tai VW.-F, Fang J, Banka AL, Roberts CD, Youngman M, Zhang H, Xiong Z, Mathis A, Pouliot JJ, Hamatake RK, Price DP, Seal JW. III, Stroup LL, Creech KL, Carballo LH, Todd D, Spaltenstein A, Furst S, Hong Z, Peat AJ. J. Med. Chem. 2014; 57: 2107
• 1b Hicken EJ, Marmsater FP, Munson MC, Schlachter ST, Robinson JE, Allen S, Burgess LE, DeLisle RK, Rizzi JP, Topalov GT, Zhao Q, Hicks JM, Kallan NC, Tarlton E, Allen A, Callejo M, Cox A, Rana S, Klopfenstein N, Woessner R, Lyssikatos JP. ACS Med. Chem. Lett. 2014; 5: 78
• 1c Reutlinger M, Rodrigues T, Schneider P, Schneider G. Angew. Chem. Int. Ed. 2014; 53: 582
• 1d Meng T, Wang W, Zhang Z, Ma L, Zhang Y, Miao Z, Shen J. Bioorg. Med. Chem. 2014; 22: 848
• 1e Gallud A, Vaillant O, Maillard LT, Arama DP, Dubois J, Maynadier M, Lisowski V, Garcia M, Martinez J, Masurier N. Eur. J. Med. Chem. 2014; 75: 382
• 1f Huang S, Qing J, Wang S, Wang H, Zhang L, Tang Y. Org. Biomol. Chem. 2014; 12: 2344
• 1g Denora N, Margiotta N, Laquintana V, Lopedota A, Cutrignelli A, Losacco M, Natile FG. ACS Med. Chem. Lett. 2014; 5: 685

For latest articles, see:
• 2a Cao H, Liu X, Zhao L, Cen J, Lin J, Zhu Q, Fu M. Org. Lett. 2014; 16: 146
• 2b Sanaeishoar T, Tavakkoli H, Mohave F. Appl. Catal. A: Gen. 2014; 470: 56
• 2c Siddiqui IR, Rai P, Rahila S, Anushree A, Shamim S. Tetrahedron Lett. 2014; 55: 1159
• 2d Wang Y, Saha B, Li F, Frett B, Li H.-Y. Tetrahedron Lett. 2014; 55: 1281
• 2e Wang S, Liu W, Cen J, Liao J, Huang J, Zhan H. Tetrahedron Lett. 2014; 55: 1589
• 2f Maleki A, Rezayan AH. Tetrahedron Lett. 2014; 55: 1848
• 2g Vidyacharan S, Shinde AH, Satpathi B, Sharada DS. Green Chem. 2014; 16: 1168
• 2h Chen C, Shang G, Zhou J, Yu Y, Li B, Peng J. Org. Lett. 2014; 16: 1872
• 2i Zheng L, Hua R. J. Org. Chem. 2014; 79: 3930
• 2j Gao Z, Zhu X, Zhang R. RSC Adv. 2014; 4: 19891
• 2k Wang Y, Frett B, Li HY. Org. Lett. 2014; 16: 3016
• 2l Xu X, Hu P, Yu W, Hong G, Tang Y, Fang M, Li X. Synlett 2014; 25: 718
• 3a Klapars A, Antilla JC, Huang X, Buchwald SL. J. Am. Chem. Soc. 2001; 123: 7727
• 3b Antilla JC, Baskin JM, Barder TE, Buchwald SL. J. Org. Chem. 2004; 69: 5578
• 3c Altman RA, Buchwald SL. Org. Lett. 2006; 8: 2779
• 4a Taillefer M, Cristau H.-J, Cellier PP, Spindler J.-F. French Patent 2840303, 2003 ; Chem. Abstr. 2003, 140, 16744.
• 4b Cristau H.-J, Cellier PP, Spindler J.-F, Taillefer M. Chem. Eur. J. 2004; 10: 5607
• 4c Cristau H.-J, Cellier PP, Spindler J.-F, Taillefer M. Eur. J. Org. Chem. 2004; 695
• 4d Taillefer M, Xia N, Ouali A. WO Patent 2008004088, 2008 ; Chem. Abstr. 2008, 148, 144205.
• 5a Enguehard C, Allouchi H, Gueiffier A, Buchwald SL. J. Org. Chem. 2003; 68: 4367
• 5b Enguehard C, Allouchi H, Gueiffier A, Buchwald SL. J. Org. Chem. 2003; 68: 5614
• 5c Enguehard-Gueiffier C, Thery I, Gueiffier A, Buchwald SL. Tetrahedron 2006; 62: 6042
• 5d Bischoff A, Subramanya H, Sundaresan K, Sammeta SR, Vaka AK (Forest Laboratories Holdings Ltd) US Patent 201000160323, 2010 ; Chem. Abstr. 2010, 153, 116278.
• 5e Terao Y, Suzuki H, Yoshikawa M, Yashiro H, Takekawa S, Fujitani Y, Okada K, Inoue Y, Yamamoto Y, Nakagawa H, Yao S, Kawamoto T, Uchikawa O. Bioorg. Med. Chem. Lett. 2012; 22: 7326
• 5f Ince S, Haegebarth A, Politz O, Neuhaus R, Boemer U, Scott W (Bayer Pharma Aktiengesellschaft) International Patent WO 2012007345, 2012 ; Chem. Abstr. 2012, 156, 203296.
• 5g Enguehard-Gueiffier C, Musiu S, Henry N, Véron J.-B, Mavel S, Neyts J, Leyssen P, Paeshuyse J, Gueiffier A. Eur. J. Med. Chem. 2013; 64: 448

For reviews and other recent articles on copper catalyst and heterocyclic compounds, see:
• 6a Hassan J, Sévignon M, Gozzi C, Schulz E, Lemaire M. Chem. Rev. 2002; 102: 1359
• 6b Schnürch M, Flasik R, Khan AF, Spina M, Mihovilovic MD, Stanetty P. Eur. J. Org. Chem. 2006; 3283
• 6c Evano G, Blanchard N, Toumi M. Chem. Rev. 2008; 108: 3054
• 6d Liang L, Li Z, Zhou X. Org. Lett. 2009; 11: 3294
• 6e Monnier F, Taillefer M. Angew. Chem. Int. Ed. 2009; 48: 6954
• 6f Bhadra S, Sreedhar B, Ranu BC. Adv. Synth. Catal. 2009; 351: 2369
• 6g Bagley MC, Davis T, Dix MC, Fusillo V, Rokicki MJ, Kipling D. J. Org. Chem. 2009; 74: 8336
• 6h Fukuzawa S.-I, Shimizu E, Atsuumi Y, Haga M, Ogata K. Tetrahedron Lett. 2009; 50: 2374
• 6i Sahoo SK, Jamir L, Guin S, Patel BK. Adv. Synth. Catal. 2010; 352: 2538
• 6j Sperotto H, van Klink GP. M, de Vries JG, van Koten G. Tetrahedron 2010; 66: 3478
• 6k Ranjit S, Lee R, Heryadi D, Shen C, Wu J.-E, Zhang P, Huang K.-W, Liu X. J. Org. Chem. 2011; 76: 8999
• 7a Kochi JK. J. Am. Chem. Soc. 1971; 93: 1487
• 7b Neumann SM, Kochi JK. J. Org. Chem. 1975; 40: 599
• 7c Smith RS, Kochi JK. J. Org. Chem. 1976; 41: 502
• 8a Su Y, Jia W, Jiao N. Synthesis 2011; 1678 ; and references cited therein
• 8b Panda N, Jena AK, Mohapatra S, Rout SR. Tetrahedron Lett. 2011; 52: 1924
• 8c Kundu D, Chatterjee T, Ranu BC. Adv. Synth. Catal. 2013; 355: 2285 ; and references cited therein
• 9 Hiebel M.-A, Fall Y, Scherrmann M.-C, Berteina-Raboin S. Eur. J. Org. Chem. 2014; 4643

For our latest articles on imidazo[1,2-a]pyridine, see:
• 10a El Akkaoui A, Bassoude I, Koubachi J, Berteina-Raboin S, Mouaddib A, Guillaumet G. Tetrahedron 2011; 67: 7128
• 10b El Kazzouli A, Berteina-Raboin S, Mouaddib A, Guillaumet G. Lett. Org. Chem. 2012; 9: 118
• 10c El Akkaoui A, Hiebel M.-A, Mouaddib A, Berteina-Raboin S, Guillaumet G. Tetrahedron 2012; 68: 9131
• 10d Arnould A, Hiebel M.-A, Massip S, Léger J.-M, Jarry C, Berteina-Raboin S, Guillaumet G. Chem. Eur. J. 2013; 19: 12249
• 11 Kondo T, Mitsudo T. Chem. Rev. 2000; 100: 3205
• 12 Hartwig JF. Inorg. Chem. 2007; 46: 1936
• 13 Bogenteatter M, Carruthers NI, Jablonowski JA, Lovenberg TW, Ly KS (Ortho McNeil Pharmaceutical, Inc.) International Patent WO 02/079168, 2002 ; Chem. Abstr. 2002, 137, 279192.
• 14 He C, Hao J, Xu H, Mo Y, Liu H, Han J, Lei A. Chem. Commun. 2012; 48: 11073
• 15 Barlin GB, Davies LP, Ireland SJ, Ngu MM. L, Zhang J. Aus. J. Chem. 1992; 45: 877
• 16 Gol’dfarb Y, Stoyanovich FM, Show A. Chem. Heterocycl. Compd. 1979; 15: 514