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Synlett 2014; 25(14): 2049-2053
DOI: 10.1055/s-0034-1378355
DOI: 10.1055/s-0034-1378355
letter
Cobalt-Catalyzed Direct Alkenylation of 2-Methylquinolines with Aldehydes via C(sp3)–H Functionalization in Water
Further Information
Publication History
Received: 07 May 2014
Accepted after revision: 31 May 2014
Publication Date:
09 July 2014 (online)
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Abstract
The direct C(sp3)–H alkenylation of 2-methylquinolines with aldehydes as a simple methodology to afford 2-alkenylated quinolines is reported. In the presence of catalytic CoCl2 in water, the economically and ecologically sound transformation is proposed to proceed via the direct benzylic addition to the aldehyde followed by an elimination step to provide 2-alkenylated quinolines in good to excellent yield of up to 95%.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/products/ejournals/journal/ 10.1055/s-00000083.
- Supporting Information
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References and Notes
-
1a Gulevich AV, Dudnik AS, Chernyak N, Gevorgyan V. Chem. Rev. 2013; 113: 3084
- 1b Sridharan V, Suryavanshi PA, Menéndez JC. Chem. Rev. 2011; 111: 7157
- 1c Cho SH, Kim JY, Kwak J, Chang S. Chem. Soc. Rev. 2011; 40: 5068
- 1d Barluenga J, Rodríguez F, Fañanás FJ. Chem. Asian J. 2009; 4: 1036
- 1e Kouznetsov VV, Méndez LY. V, Gómez CM. M. Curr. Org. Chem. 2005; 9: 141
-
2a Jazzar R, Hitce J, Renaudat A, Sofack-Kreutzer J, Baudoin O. Chem. Eur. J. 2010; 16: 2654
- 2b Thansandote P, Lautens M. Chem. Eur. J. 2009; 15: 5874
- 2c Tobisu M, Chatani N. Angew. Chem. Int. Ed. 2006; 45: 1683
- 2d Godula K, Sames D. Science 2006; 312: 67
- 2e Kakiuchi F, Chatani N. Adv. Synth. Catal. 2003; 345: 1077
- 3a Guan B.-T, Hou Z. J. Am. Chem. Soc. 2011; 133: 18086
- 3b Mousseau JJ, Bull JA, Charette AB. Angew. Chem. Int. Ed. 2010; 49: 1115
- 3c Wu J, Cui X, Chen L, Jiang G, Wu Y. J. Am. Chem. Soc. 2009; 131: 13888
- 3d Tobisu M, Hyodo I, Chatani N. J. Am. Chem. Soc. 2009; 131: 12070
- 3e Nakao Y, Kanyiva KS, Hiyama T. J. Am. Chem. Soc. 2008; 130: 2448
- 3f Larivée A, Mousseau JJ, Charette AB. J. Am. Chem. Soc. 2007; 130: 52
- 3g Kanyiva KS, Nakao Y, Hiyama T. Angew. Chem. Int. Ed. 2007; 46: 8872
- 3h Leclerc J.-P, Fagnou K. Angew. Chem. Int. Ed. 2006; 45: 7781
- 3i Campeau L.-C, Rousseaux S, Fagnou K. J. Am. Chem. Soc. 2005; 127: 18020
- 4a Li Y, Guo F, Zha Z, Wang Z. Chem. Asian J. 2013; 8: 534
- 4b Graves VB, Shaikh A. Tetrahedron Lett. 2013; 54: 695
- 4c Jin J.-J, Niu H.-Y, Qu G.-R, Guo H.-M, Fossey JS. RSC Adv. 2012; 2: 5968
- 4d Rueping M, Tolstoluzhsky N. Org. Lett. 2011; 13: 1095
- 4e Qian B, Xie P, Xie Y, Huang H. Org. Lett. 2011; 13: 2580
- 4f Komai H, Yoshino T, Matsunaga S, Kanai M. Org. Lett. 2011; 13: 1706
- 4g Qian B, Guo S, Xia C, Huang H. Adv. Synth. Catal. 2010; 352: 3195
- 4h Qian B, Guo S, Shao J, Zhu Q, Yang L, Xia C, Huang H. J. Am. Chem. Soc. 2010; 132: 3650
- 5a Yan G, Wu X, Yang M. Org. Biomol. Chem. 2013; 11: 5558
- 5b Ogata Y, Kawasaki A, Hirata H. J. Chem. Soc., Perkin Trans. 2 1972; 1120
- 5c Kaslow CE, Stayner RD. J. Am. Chem. Soc. 1945; 67: 1716
- 6a Miao C.-X, Wang J.-Q, Wu Y, Du Y, He L.-N. ChemSusChem 2008; 1: 236
- 6b Lin Y.-M, Boucau J, Li Z, Casarotto V, Lin J, Nguyen AN, Ehrmantraut J. Org. Lett. 2007; 9: 567
- 6c Huber A, Müller L, Elias H, Klement R, Valko M. Eur. J. Inorg. Chem. 2005; 1459
- 6d Harrowven DC, Nunn MI. T, Blumire NJ, Fenwick DR. Tetrahedron 2001; 57: 4447
- 6e Kobayashi S, Busujima T, Nagayama S. Chem. Eur. J. 2000; 6: 3491
- 7a Butler RN, Coyne AG. Chem. Rev. 2010; 110: 6302
- 7b Herrerías CI, Yao X, Li Z, Li C.-J. Chem. Rev. 2007; 107: 2546
- 8 Bull JA, Mousseau JJ, Pelletier G, Charette AB. Chem. Rev. 2012; 112: 2642
- 9a Halama A, Jirman J, Boušková O, Gibala P, Jarrah K. Org. Process Res. Dev. 2010; 14: 425
- 9b Liang J, Lalonde J, Borup B, Mitchell V, Mundorff E, Trinh N, Kochrekar DA, Nair Cherat R, Pai GG. Org. Process Res. Dev. 2009; 14: 193
- 9c Merschaert A, Boquel P, Van Hoeck J.-P, Gorissen H, Borghese A, Bonnier B, Mockel A, Napora F. Org. Process Res. Dev. 2006; 10: 776
- 9d Larsen RD, Corley EG, King AO, Carroll JD, Davis P, Verhoeven TR, Reider PJ, Labelle M, Gauthier JY, Xiang YB, Zamboni RJ. J. Org. Chem. 1996; 61: 3398
- 9e Labelle M, Belley M, Gareau Y, Gauthier JY, Guay D, Gordon R, Grossman SG, Jones TR, Leblanc Y, McAuliffe M, McFarlane C, Masson P, Metters KM, Ouimet N, Patrick DH, Piechuta H, Rochette C, Sawyer N, Xiang YB, Pickett CB, Ford-Hutchinson AW, Zamboni RJ, Young RN. Bioorg. Med. Chem. Lett. 1995; 5: 283
- 9f King AO, Corley EG, Anderson RK, Larsen RD, Verhoeven TR, Reider PJ, Xiang YB, Belley M, Leblanc Y. J. Org. Chem. 1993; 58: 3731
- 9g McNamara JM, Leazer JL, Bhupathy M, Amato JS, Reamer RA, Reider PJ, Grabowski EJ. J. J. Org. Chem. 1989; 54: 3718
- 10 General Procedure To an 8 mL screw-capped reaction vial equipped with a magnetic stirrer bar, CoCl2 (1.3 mg, 2.0 mol%), 2-methyl-quinoline (0.5 mmol), aldehyde (1.0 mmol), and H2O (0.3 mL) were added. The resulting mixture was placed into a preheated oil bath at 120 °C with vigorous stirring. After 24 h, the reaction mixture was removed from the oil bath, allowed to cool to r.t. and poured into H2O (10 mL). The mixture was then extracted with EtOAc (3 × 20 mL), washed with brine (40 mL), dried over Na2SO4, filtered, and the solvent removed under reduced pressure. The crude product was then loaded onto a column of silica gel suspended in hexane. Purification by flash chromatography (hexane–EtOAc = 95:5, v/v) then gave the pure alkenylation product. (E)-2-(4-Bromostyryl)quinoline (3ad) Pale yellow solid in 91% yield (141.8 mg). 1H NMR (400 MHz, CDCl3): δ = 8.08 (d, J = 8.4 Hz, 2 H), 7.76 (d, J = 8.0 Hz, 1 H), 7.70 (t, J = 7.62 Hz, 1 H), 7.62–7.58 (m, 2 H), 7.51–7.45 (m, 5 H), 7.35 (d, J = 16.4 Hz, 1 H). 13C NMR (100 MHz, CDCl3): δ = 155.6, 148.3, 136.5, 135.5, 133.1, 132.0, 129.9, 129.7, 129.3, 128.7, 127.5, 127.4, 126.3, 122.6, 119.4. ESI-HRMS: m/z calcd for C17H13BrN [M + H]: 310.0231; found: 310.0234. (E)-2-[2-(Pyridin-3-yl)vinyl]quinoline (5ad) Pale yellow solid in 86% yield (100.2 mg). 1H NMR (400 MHz, CDCl3): δ = 8.83 (s, 1 H), 8.54 (s, 1 H), 8.10 (dd, J 1 = 8.4 Hz, J 2 = 12.2 Hz, 2 H), 7.92 (d, J = 8.0 Hz, 1 H), 7.78–7.61 (m, 4 H), 7.50 (t, J = 7.4 Hz, 1 H), 7.42 (d, J = 16.4 Hz, 1 H), 7.30 (dd, J 1 = 5.2 Hz, J 2 = 8.0 Hz 1 H). 13C NMR (100 MHz, CDCl3): δ = 155.2, 149.4, 149.2, 148.2, 136.6, 133.3, 132.3, 130.9, 130.6, 129.9, 129.3, 127.55, 127.52, 126.5, 123.7, 119.4. ESI-HRMS: m/z calcd for C16H13N2 [M + H]: 233.1078; found: 233.1075. (E)-8-Chloro-2-styrylquinoline (3da) This compound was prepared in a similar procedure to the general procedure with 5.0 mol% CoCl2 at 140 °C for 48 h to afford a pale yellow solid in 84% yield (111.3 mg). 1H NMR (400 MHz, CDCl3): δ = 8.09 (d, J = 8.8 Hz, 1 H), 7.81 (dd, J 1 = 1.0 Hz, J 2 = 7.4 Hz, 1 H), 7.75 (d, J = 16.4 Hz, 1 H), 7.70–7.64 (m, 4 H), 7.48–7.32 (m, 5 H). 13C NMR (100 MHz, CDCl3): δ = 156.6, 144.4, 136.6, 136.3, 135.3, 133.3, 129.8, 128.8, 128.75, 128.73, 128.5, 127.4, 126.6, 125.9, 120.0. ESI-HRMS: m/z calcd for C17H13ClN [M + H]: 266.0736; found: 266.0739.