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Synlett 2016; 27(09): 1408-1412
DOI: 10.1055/s-0035-1561382
DOI: 10.1055/s-0035-1561382
letter
Copper-Catalyzed Imino C–N Bond Formation with Aryl Boronic Acids under Aerobic Conditions
Further Information
Publication History
Received: 17 October 2015
Accepted after revision: 18 January 2016
Publication Date:
18 February 2016 (online)
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Abstract
A copper-catalyzed, ligand- and base-free C–N cross-coupling reaction of iminochromenes with arylboronic acids in a nontoxic ethanol solvent at room temperature under air is developed. The product yields are found to be good to moderate. The conservation of the sensitive imine functional group implies the mildness of this protocol
Supporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0035-1561382.
- Supporting Information
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References and Notes
- 1 Also called iminocoumarins.
- 2a Wang JL, Liu D, Zhang Z, Shan S, Han X, Srinvasula SM, Croce CM, Alnemeri ES, Huang Z. Proc. Natl. Acad. Sci. U.S.A. 2000; 97: 7124
- 2b Hadfield JA, Pavlidis VH, Perry PJ, Mc Gown AT. Anticancer Drugs 1999; 10: 591
- 2c Huang CK, Wu FY, Ai YX. Bioorg. Med. Chem. Lett. 1995; 5: 2423
- 2d Burke TR. Jr, Lim B, Marquez VE, Li ZH, Bolen JB, Stefanova I, Horak ID. J. Med. Chem. 1993; 36: 425
- 2e O’Callaghan CN, Conalty ML. Proc. R. Ir. Acad., Sect. B 1983; 83: 241
- 2f O’Callaghan CN. Proc. R. Ir. Acad., Sect. B 1973; 73: 291
- 3a Tangmouo JG, Meli AL, Komguem J, Kuete V, Ngounou FN, Lontsi D, Beng VP, Choudhary MI, Sondengam BL. Tetrahedron Lett. 2006; 47: 3067
- 3b Abd-El-Aziz AS, El-Agrody AM, Bedair AH, Corkery TC, Ata A. Heterocycles 2004; 63: 1793
- 3c Kraus GA, Kim I. J. Org. Chem. 2003; 68: 4517
- 3d Khafagy MM, Abd El-Wahab AH. F, Eid FA, El-Agrody AM. Farmaco 2002; 57: 715
- 3e El-Agrody AM, El-Latif MS. A, El-Hady NA, Fakary AH, Bedair AH. Molecules 2001; 6: 519
- 3f Manrao MR, Singh B, Sharma JR, Kalsi PS. J. Indian Counc. Chem. 1996; 12: 38
- 4a Kitamura RO. S, Romoff P, Young MC. M, Kato MJ, Lago JH. G. Phytochemistry 2006; 67: 2398
- 4b Iqbal MC. M, Jayasinghe UL. B, Herath HM. T. B, Wijesekara KB, Fujimoto Y. Phytoparasitica 2004; 32: 119
- 4c Ukhov SV, Kon’shin ME, Odegova TF. Pharm. Chem. J. 2001; 35364
- 4d Sardari S, Nishibe S, Daneshtalab M. Stud. Nat. Prod. Chem. 2000; 23: 335
- 4e Bylov IE, Vasylyev MV, Bilokin YV. Eur. J. Med. Chem. 1999; 34: 997
- 4f Manrao MR, Goel R, Sethi RK, Kalsi PS. Indian J. Heterocycl. Chem. 1995; 4: 231
- 5 Anderson DR, Hegde S, Reinhard E, Gomez L, Vernier WF, Lee L, Liu S, Sambandam A, Snider PA, Masih L. Bioorg. Med. Chem. Lett. 2005; 15: 1587
- 6a Hill TA, Mariana A, Gordon CP, Odell LR, Robertson MJ, McGeachie AB, Chau N, Daniel JA, Gorgani NN, Robinson PJ, McCluskey A. J. Med. Chem. 2010; 53: 4094
- 6b Burke TR. Jr, Fesen M, Mazumder A, Yung J, Wang J, Carothers AM, Grunberger D, Driscoll J, Pommier Y, Kohn K. J. Med. Chem. 1995; 38: 4171
- 7a Khemakhem K, Souli M, Brousses R, Ammar H, Abid S, Fery SF. Chem. Eur. J. 2015; 21: 7927
- 7b Guo D, Chen T, Ye D, Xu J, Jiang H, Chen K, Wang H, Liu H. Org. Lett. 2011; 13: 2884
- 7c Komatsu K, Urano Y, Kojima H, Nagano T. J. Am. Chem. Soc. 2007; 129: 13447
- 7d Liepouri F, Foukaraki E, Deligeorgiev TG, Katerinopoulos HE. Cell Calcium 2001; 30: 331
- 8 Frath D, Poirel A, Ulrich G, Nicola AD, Ziessel R. Chem. Commun. 2013; 49: 4908
- 9a Yu J, Shirota Y. Chem. Lett. 2002; 10: 984
- 9b Nikolov P, Tyutyulkov N, Dryanska V. Z. Naturforsch. 1987; 42: 987
- 9c Asimov MM, Nikitchenko VM, Novikov AI, Rubinov AN, Bor Z, Gaty L. Chem. Phys. Lett. 1988; 149: 140
- 10 Kand D, Mandal PS, Datar A, Talukdar P. Dyes Pigm. 2014; 106: 25
- 11 Mishra PK, Saha T, Talukdar P. Org. Biomol. Chem. 2015; 13: 7430
- 12a Endo S, Hu D, Suyama M, Matsunaga T, Sugimoto K, Matsuya Y, Kabbani OE, Kuwata K, Hara A, Kitade Y, Toyooka N. Bioorg. Med. Chem. 2013; 21: 6378
- 12b Borisov AV, Dzhavakhishvili SG, Zhuravel IO, Kovalenko SM, Nikitchenko VM. J. Comb. Chem. 2007; 9: 5
- 12c Emary TI. E, Khalil A, Ali GA. M. E. H, Adasy AA. A. M. E. Phosphorus, Sulfur Silicon Relat. Elem. 2005; 180: 19
- 12d Volmajer J, Toplak R, Leban I, Marechal AM. L. Tetrahedron 2005; 61: 7012
- 12e Volmajer J, Toplak R, Bittner S, Leban I, Le Marechal AM. Tetrahedron Lett. 2003; 44: 2363
- 12f Mhiri CR, Gharbi RE, Bigot YL. Synth. Commun. 1999; 29: 3385
- 12g Freeman F. Chem. Rev. 1969; 69: 591
- 13a Mandal PK. RSC Adv. 2014; 4: 5803
- 13b Murugavel G, Punniyamurthy T. Org. Lett. 2013; 15: 3828
- 13c Qian W, Amegadzie A, Winternheimer D, Allen J. Org. Lett. 2013; 15: 2986
- 13d Cui S, Feng LX, Wang YG. Org. Lett. 2006; 8: 4517
- 14a Chan DM. T, Monaco KL, Wang RP, Winters MP. Tetrahedron Lett. 1998; 39: 2933
- 14b Lam PY. S, Clark CG, Saubern S, Adams J, Winters MP, Chan DM. T, Combs A. Tetrahedron Lett. 1998; 39: 2941
- 14c Evans DA, Katz JL, West TR. Tetrahedron Lett. 1998; 39: 2937
- 14d Qiao JX, Lam PY. S. Synthesis 2011; 829
- 14e Rao KS, Wu TS. Tetrahedron 2012; 68: 7735
-
14f Ley SV, Thomas AW. Angew. Chem. Int. Ed. 2003; 42: 5400
- 14g Qiao JX, Lam PY. S In Boronic Acids: Preparation and Applications in Organic Synthesis Medicine and Materials. Hall DG. Wiley-VCH; Weinheim: 2011. Vol. 2, 315
- 14h Chan DM. T, Lam PY. S In Boronic Acids: Preparation and Applications in Organic Synthesis, Medicine and Materials . Hall DG. Wiley-VCH; Weinheim: 2005: 205
- 15 Patil M, Kapdi AR, Kumar AV. RSC Adv. 2015; 5: 54505
- 16 General Procedure for the Copper-Catalyzed Coupling of Iminochromene with Arylboronic Acids To a round-bottomed flask equipped with a stir bar, the iminochromene (1 mmol), Cu(OAc)2·H2O (20 mol%), and arylboronic acid (2.3 mmol) were added. EtOH (5 mL) was added, and the reaction mixture was stirred for 24 h at r.t. After completion of the reaction as monitored by TLC, the organic phase was concentrated under reduced pressure, and the solid residue was fractioned in EtOAc (20 mL) and H2O (10 mL) thrice. The organic phase was separated and dried on anhydrous Na2SO4. The solvent was removed in vacuum, and the crude residue was purified by column chromatography with EtOAc–PE to afford the respective N-arylated chromene. Physical and spectroscopic data given below are for compound 3a and may be taken as representative. For further details, see the Supporting Information. (Z)-N-3-Diphenyl-2H-chromen-2-imine (3a) Yellow solid (249 mg, 93% yield); mp 112–113 °C. IR (KBr): ν = 1737, 1643, 1587, 1485, 1365, 1230, 1116 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.79–7.72 (m, 2 H), 7.46–7.30 (m, 7 H), 7.29 (s, 1 H), 7.20–7.13 (m, 2 H), 7.13–7.05 (m, 1 H), 7.02 (d, J = 8.2 Hz, 1 H). 13C NMR (100 MHz, CDCl3): δ = 152.9, 148.9, 146.6, 136.7, 133.6, 133.3, 132.1, 130.1, 129.1, 128.7, 128.4, 128.3, 128.0, 127.2, 123.9, 123.4, 122.8, 122.5, 120.4, 115.6, 115.3. ESI-HRMS: m/z calcd for C21H16NO [M + H]+ : 298.1226; found: 298.1277.
- 17 See the Supporting Information.
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