Copper-Catalyzed Regioselective C–H Iodination of Aromatic Carboxamides

Chuanguang Wu; Hui Zhou; Qiaolin Wu; Mina He; Pei Li; Qing Su; Ying Mu

doi:10.1055/s-0035-1561335

Synlett, Inhaltsverzeichnis

Synlett 2016; 27(06): 868-875
DOI: 10.1055/s-0035-1561335

letter

Copper-Catalyzed Regioselective C–H Iodination of Aromatic Carboxamides

Chuanguang Wu

^aCollege of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, P. R. of China eMail: wuql@jlu.edu.cn eMail: suqing@jlu.edu.cn

,

Hui Zhou

^aCollege of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, P. R. of China eMail: wuql@jlu.edu.cn eMail: suqing@jlu.edu.cn

,

Qiaolin Wu*

^aCollege of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, P. R. of China eMail: wuql@jlu.edu.cn eMail: suqing@jlu.edu.cn

,

Mina He

^aCollege of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, P. R. of China eMail: wuql@jlu.edu.cn eMail: suqing@jlu.edu.cn

,

Pei Li

^aCollege of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, P. R. of China eMail: wuql@jlu.edu.cn eMail: suqing@jlu.edu.cn

,

Qing Su*

^aCollege of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, P. R. of China eMail: wuql@jlu.edu.cn eMail: suqing@jlu.edu.cn

^cState Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian116024, P. R. of China

,

Ying Mu

^aCollege of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, P. R. of China eMail: wuql@jlu.edu.cn eMail: suqing@jlu.edu.cn

^bState Key Laboratory of Supramolecular Structure and Materials, Jilin University, 2699 Qianjin Street, Changchun 130012, P. R. of China

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Abstract

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Abstract

A concise and efficient copper-catalyzed C–H iodination of 8-aminoquinoline-based aromatic carboxamides was reported. The reaction has the broad substrate scope and shows moderate to high yields, also offers other attractive advantages including simplicity of operation, compatibility with heteroarenes, and the use of low-cost copper catalyst. The new approach was further applied to cyanation of N-(quinolin-8-yl)benzamide, offering a potentially attractive alternative to the synthesis of aromatic nitriles.

Key words

aryl halide - aromatic carboxamides - C–H halogenation - copper catalyst - heteroarenes - regioselective iodination

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Referenzen

References and Notes

1a Bergman RG. Nature (London, U.K.) 2007; 446: 391
1b Wencel-Delord J, Glorius F. Nat. Chem. 2013; 5: 369
1c Ackermann L. Chem. Rev. 2011; 111: 1315
1d Engle KM, Mei T.-S, Wasa M, Yu J.-Q. Acc. Chem. Res. 2012; 45: 788
1e Li B.-J, Shi Z.-J. Chem. Soc. Rev. 2012; 41: 5588

2a Hartwig JF. Nature (London, U.K.) 2008; 455: 314
2b Daugulis O, Do H.-Q, Shabashov D. Acc. Chem. Res. 2009; 42: 1074
2c Chen X, Engle KM, Wang D.-H, Yu J.-Q. Angew. Chem. Int. Ed. 2009; 48: 5094
2d Yoo EJ, Ma S, Mei T.-S, Chan KS. L, Yu J.-Q. J. Am. Chem. Soc. 2011; 133: 7652
2e Mu X, Wu T, Wang H, Guo Y, Liu G. J. Am. Chem. Soc. 2012; 134: 878
2f Shi Z, Suri M, Glorius F. Angew. Chem. Int. Ed. 2013; 52: 4892
2g Yan J.-X, Li H, Liu X.-W, Shi J.-L, Wang X, Shi Z.-J. Angew. Chem. Int. Ed. 2014; 53: 4945

3a Dick AR, Hull KL, Sanford MS. J. Am. Chem. Soc. 2004; 126: 2300
3b Wan XB, Ma ZX, Li BJ, Zhang KY, Cao SK, Zhang SW, Shi ZJ. J. Am. Chem. Soc. 2006; 128: 7416
3c Zhao XD, Dimitrijević E, Dong VM. J. Am. Chem. Soc. 2009; 131: 3466
3d Wang X.-C, Hu Y, Bonacorsi S, Hong Y, Burrell R, Yu J.-Q. J. Am. Chem. Soc. 2013; 135: 10326
3e Chu L, Wang X.-C, Moore CE, Rheingold AL, Yu J.-Q. J. Am. Chem. Soc. 2013; 135: 16344
3f Moyano A, Rosol M, Moreno RM, Lopez C, Maestro MA. Angew. Chem. Int. Ed. 2005; 44: 1865
3g Mei T.-S, Giri R, Maugel N, Yu J.-Q. Angew. Chem. Int. Ed. 2008; 47: 5215
3h Sun X, Sun Y, Zhang C, Rao Y. Chem. Commun. 2014; 50: 1262
3i Du B, Jiang X, Sun P. J. Org. Chem. 2013; 78: 2786
3j Kalyani D, Dick AR, Anani WQ, Sanford MS. Org. Lett. 2006; 8: 2523
3k Song B, Zheng X, Mo J, Xu B. Adv. Synth. Catal. 2010; 352: 329

4a Silverman GS, Rakita PE. Handbook of Grignard Reagents. Marcel Dekker; New York: 1996
4b Nicolaou KC, Bulger PG, Sarlah D. Angew. Chem. Int. Ed. 2005; 44: 4442
4c Hassan J, Vignon M, Gozzi C, Schulz E, Lemaire M. Chem. Rev. 2002; 102: 1359

5a Beak P, Snieckus V. Acc. Chem. Res. 1982; 15: 306
5b Snieckus V. Chem. Rev. 1990; 90: 879
5c Gilman H, Dietrich JJ. J. Am. Chem. Soc. 1957; 79: 1439
5d Merkushev EB. Synthesis 1988; 923

6 Chen X, Hao X.-S, Goodhue CE, Yu J.-Q. J. Am. Chem. Soc. 2006; 128: 6790
7 Yang L, Lu Z, Stahl SS. Chem. Commun. 2009; 42: 6460
8 Yao B, Wang ZL, Zhang H, Wang DX, Zhao LM, Wang X. J. Org. Chem. 2012; 77: 3336
9 Truong T, Klimovica K, Daugulis O. J. Am. Chem. Soc. 2013; 135: 9342

10a Tran LD, Popov I, Daugulis O. J. Am. Chem. Soc. 2012; 134: 18237
10b Suess AM, Ertem MZ, Cramer CJ, Stahl SS. J. Am. Chem. Soc. 2013; 135: 9797
10c Shang M, Sun S.-Z, Dai H.-X, Yu J.-Q. J. Am. Chem. Soc. 2014; 136: 3354
10d Zhang Q, Chen K, Rao W.-H, Zhang Y.-J, Chen F.-J, Shi B.-F. Angew. Chem. Int. Ed. 2013; 52: 13588
10e Wang Z, Ni J.-Z, Kuninobu Y, Kanai M. Angew. Chem. Int. Ed. 2014; 53: 3496
10f Wu X, Zhao Y, Zhang G, Ge H. Angew. Chem. Int. Ed. 2014; 53: 3706
10g Li X, Liu Y.-H, Gu W.-J, Li B, Chen F.-J, Shi B.-F. Org. Lett. 2014; 16: 3904
10h Li Q, Zhang S.-Y, He G, Ai Z, Nack WA, Chen G. Org. Lett. 2014; 16: 1764
10i Urones B, Martínez AM, Rodríguez N, Arrayás RG, Carretero JC. Chem. Commun. 2013; 49: 11044

11a Ding ST, Jiao N. J. Am. Chem. Soc. 2011; 133: 12374
11b Kim J, Choi J, Shin K, Chang S. J. Am. Chem. Soc. 2012; 134: 2528
11c Gong T.-J, Xiao B, Cheng W.-M, Su W, Xu J, Liu Z.-J, Liu L, Fu Y. J. Am. Chem. Soc. 2013; 135: 10630
11d Sundermeier M, Zapf A, Beller M. Angew. Chem. Int. Ed. 2003; 42: 1661
11e Wen Q, Jin J, Mei Y, Lu P, Wang Y. Eur. J. Org. Chem. 2013; 4032
11f Okamoto K, Watanabe M, Murai M, Hatano R, Ohe K. Chem. Commun. 2012; 48: 3127

12a Amantini D, Beleggia R, Fringuelli F, Pizzo F, Vaccaro L. J. Org. Chem. 2004; 69: 2896
12b Jia X, Yang D, Zhang S, Cheng J. Org. Lett. 2009; 11: 4716
12c Hong X, Wang H, Qian G, Tan Q, Xu B. J. Org. Chem. 2014; 79: 3228

13a Yeung CS, Dong VM. Chem. Rev. 2011; 111: 1215
13b Cho SH, Kim JY, Kwak J, Chang S. Chem. Soc. Rev. 2011; 40: 5068
13c Hull KL, Sanford MS. J. Am. Chem. Soc. 2007; 129: 11904
13d Li B.-J, Tian S.-L, Fang Z, Shi Z.-J. Angew. Chem. Int. Ed. 2008; 47: 1115
13e Wei Y, Su W. J. Am. Chem. Soc. 2010; 132: 16377

14a Hewgley JB, Stahl SS, Kozlowski MC. J. Am. Chem. Soc. 2008; 130: 12232
14b Do H.-Q, Daugulis O. J. Am. Chem. Soc. 2009; 131: 17052
14c Roithová J, Schröder D. Chem. Eur. J. 2008; 14: 2180
14d Monguchi D, Yamamura A, Fujiwara T, Somete T, Mori A. Tetrahedron Lett. 2010; 51: 850
14e Wendlandt AE, Suess AM, Stahl SS. Angew. Chem. Int. Ed. 2011; 50: 11062

15a Rouquet G, Chatani N. Angew. Chem. Int. Ed. 2013; 52: 11726
15b John A, Nicholas KM. J. Org. Chem. 2011; 76: 4158
15c Takamatsu K, Hirano K, Satoh T, Miura M. Org. Lett. 2014; 16: 2892
15d Chen X, Dobereiner G, Hao X.-S, Giri R, Mauel N, Yu J.-Q. Tetrahedron 2009; 65: 3085

16a Casitas A, Canta M, Solá M, Costas M, Ribas X. J. Am. Chem. Soc. 2011; 133: 19386
16b Nishino M, Hirano K, Satoh T, Miura M. Angew. Chem. Int. Ed. 2013; 52: 1

17a Tran LD, Roane J, Daugulis O. Angew. Chem. Int. Ed. 2013; 52: 6043
17b Dong J, Wang F, You J. Org. Lett. 2014; 16: 2884

18a Ribas X, Jackson DA, Donnadieu B, Mahía J, Parella T, Xifra R, Hedman B, Hodgson KO, Llobet A, Stack TD. P. Angew. Chem. Int. Ed. 2002; 41: 2991
18b King AE, Huffman LM, Casitas A, Costas M, Ribas X, Stahl SS. J. Am. Chem. Soc. 2010; 132: 12068
18c Wang Z.-L, Zhao L, Wang M.-X. Org. Lett. 2011; 13: 6560

19a Maeda H, Ishikawa Y, Matsuda T, Osuka A, Furuta H. J. Am. Chem. Soc. 2003; 125: 11822
19b Ribas X, Xifra R, Parella T, Poater A, Solà M, Llobet A. Angew. Chem. Int. Ed. 2006; 45: 2941
19c Chmielewski PJ, Latos-Grażyński L, Schmidt I. Inorg. Chem. 2000; 39: 5475
19d Yao B, Wang D.-X, Huang Z.-T, Wang M.-X. Chem. Commun. 2009; 2899
19e Zhang H, Zhao L, Wang D-X, Wang M.-X. Org. Lett. 2013; 15: 3836

20 The Preparation of Aromatic Carboxamide – General Procedure To a 50 mL three-necked flask, isonicotinic acid (2.5 g, 20 mmol), DMF (5 drops), and anhydrous CH₂Cl₂ (30 mL) were added under a N₂ atmosphere. Oxalyl chloride (2.1 mL, 24 mmol, 1.2 equiv) was added dropwise at 0 °C resulting in vigorous bubbling. The mixture was stirred for 5 h at room temperature, and the solvent was then removed in vacuo. The resulting acid chloride was used immediately without further purification. To a 100 mL three-necked flask, 8-aminoquinoline (3.8 g, 26 mmol, 1.3 equiv), Et₃N (5.7 mL, 40 mmol, 2 equiv), and anhydrous CH₂Cl₂ (30 mL) were added. A solution of the acid chloride in anhydrous CH₂Cl₂ (10 mL) was added dropwise to the solution at 0 °C, and the solution was then warmed to room temperature. After stirring overnight, the reaction system was quenched with NaHCO₃ (30 mL of sat. aq solution) and the organic layer was separated. The aqueous layer was extracted with CH₂Cl₂ (2 × 15 mL). The combined organic layers were washed with aq HCl (30 mL, 1 M) and brine (30 mL), dried over MgSO₄, filtered, and evaporated in vacuo. The obtained crude amide was purified by column chromatography on silica gel (eluant: CH₂Cl₂–PE = 5:1) to afford the desired amide. Copper-Catalyzed C–H Iodination of Aromatic Carboxamides; General Procedure A mixture of 1 (74.5 mg, 0.3 mmol), I₂ (76.2 mg, 0.3 mmol), PhI(OAc)₂ (193.2 mg, 0.6 mmol), and Cu(OAc)₂ (10.9 mg, 0.06 mmol) in NMP (2 mL) was stirred at 100 °C under O₂ (1 atm) for 20 h. The reaction mixture was cooled to room temperature and diluted with CH₂Cl₂ (2 mL). The suspension was filtered through a pad of Celite, and the residue was washed three times with CH₂Cl₂ (3 × 5 mL). The filtrate was concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography to afford the desired product. Analytical Data of Some Typical Compounds 4-Methyl-N-(quinolin-8-yl)benzamide (2) Brown solid (yield, 62%). ¹H NMR (300 MHz, CDCl₃): δ = 10.72 (s, 1 H), 8.92 (d, 1 H), 8.85 (d, 1 H), 8.21 (d, 1 H), 8.0 (d, 2 H) 7.62–7.47 (m, 3 H), 7.34 (d, 3 H), 2.45 (s, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 165.18, 148.48, 142.14, 140.33, 139.10, 138.16, 135.50, 131.95, 131.01, 129.30, 127.12, 122.96, 117.67, 89.01, 21.50. ESI-HRMS: m/z calcd for C₁₇H₁₄N₂O [M + H]⁺: 263.1179; found: 263.1227. 4-Methyl-N-(5-iodoquinolin-8-yl)benzamide (2a) White solid (yield, 93%). ¹H NMR (300 MHz, CDCl₃): δ = 10.73 (s, 1 H), 8.86–8.82 (m, 1 H), 8.75–8.69 (d, 2 H), 8.44–8.37 (m, 1 H), 8.16 (d, 1 H), 8.00–7.92 (d, 2 H), 7.60–7.54 (m, 1 H), 7.39–7.32 (d, 2 H), 2.45 (s, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 165.16, 148.58, 140.53, 138.16, 131.92, 131.95, 129.30, 129.47, 127.12, 122.95, 117.67, 89.91, 21.35. ESI-HRMS: m/z calcd for C₁₇H₁₃IN₂O [M + H]⁺: 389.0145; found: 389.0160. N-(5-Iodoquinolin-8-yl)isonicotinamide (9a) White solid (yield, 75%). ¹H NMR (300 MHz, CDCl₃): δ = 10.82 (s, 1 H), 8.87–8.84 (m, 3 H), 8.69 (d, 1 H), 8.43 (d, 1 H), 8.16 (d, 1 H), 7.91 (d, 2 H), 7.62–7.59 (m, 1 H). ¹³C NMR (75 MHz, CDCl₃): δ = 163.18, 150.66, 149.14, 142.06, 140.98, 139.18, 138.27, 134.70, 129.77, 123.49, 121.20, 118.25, 90.64. ESI-HRMS: m/z calcd for C₁₅H₁₀N₃O [M + H]⁺: 375.9941; found: 375.9970. 3-Iodo-N-(5-iodoquinolin-8-yl)isonicotinamide (9b) Brown solid (yield, 17%). ¹H NMR (300 MHz, CDCl₃): δ = 10.23 (s, 1 H), 9.10 (d, 1 H), 8.76 (s, 1 H), 8.70 (d, 1 H), 8.66 (d, 1 H), 8.40 (d, 1 H), 8.16 (d, 1 H), 7.57–7.54 (m, 2 H). ¹³C NMR (75 MHz, CDCl₃): δ = 164.95, 158.74, 149.40, 149.14, 148.31, 140.89, 138.99, 138.18, 134.57, 129.77, 123.47, 122.74, 118.43, 91.50, 90.97. ESI-HRMS: m/z calcd for C₁₅H₉N₃O [M + H]⁺: 501.8908; found: 501.8941.

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