Rhodium(III)-Catalyzed Oxidative Olefination of N-(Naphthalen-1-yl)amides

Abstract

Rhodium(III)-catalyzed oxidative coupling of N-(naphthalen-1-yl)amides with acrylates and styrene was achieved through selective C–H bond activation at the peri position. This reaction proceeded smoothly to give the direct olefination product or the corresponding olefination–cyclization product. High functional-group tolerance was observed

Keywords

oxidative olefination - C–H activation - rhodium

• References

• 1a Jia C, Kitamura T, Fujiwara Y. Acc. Chem. Res 2001; 34: 633
• 1b Fujiwara Y, Moritani I, Matsuda M, Teranishi S. Tetrahedron Lett. 1968; 9: 633
• 1c Moritanl I, Fujiwara Y. Tetrahedron Lett. 1967; 8: 1119
• 2a Baran PS, Corey EJ. J. Am. Chem. Soc. 2002; 124: 7904
• 2b Beck EM, Hatley R, Gaunt MJ. Angew. Chem. Int. Ed. 2008; 47: 3004
• 2c Cushing TD, Sanz-Cervera JF, Williams RM. J. Am. Chem. Soc. 1993; 115: 9323
• 2d Garg NK, Caspi DD, Stoltz BM. J. Am. Chem. Soc. 2004; 126: 9552
• 2e Trost BM, Godleski SA, Genet JP. J. Am. Chem. Soc. 1978; 100: 3930
• 3a Wencel-Delord J, Dröge T, Liu F, Glorius F. Chem. Soc. Rev. 2011; 40: 4740
• 3b Yeung CS, Dong VM. Chem. Rev. 2011; 111: 1215
• 4 Weissman H, Song X, Milstein D. J. Am. Chem. Soc. 2000; 123: 337
• 5a Colby DA, Bergman RG, Ellman JA. Chem. Rev. 2009; 110: 624
• 5b Satoh T, Miura M. Chem.–Eur. J. 2010; 16: 11212
• 5c Song G, Wang F, Li X. Chem. Soc. Rev. 2012; 41: 3651
• 5d Zhu C, Wang R, Falck JR. Chem.–Asian J. 2012; in press;
• 6 Mochida S, Umeda N, Hirano K, Satoh T, Miura M. Chem. Lett. 2010; 39: 744
• 7a Besset T, Kuhl N, Patureau FW, Glorius F. Chem.–Eur. J. 2011; 17: 7167
• 7b Patureau FW, Besset T, Glorius F. Angew. Chem. Int. Ed. 2011; 50: 1064
• 7c Patureau FW, Glorius F. J. Am. Chem. Soc. 2010; 132: 9982
• 7d Wencel-Delord J, Nimphius C, Patureau FW, Glorius F. Angew. Chem. Int. Ed. 2012; 51: 2247
• 7e Wencel-Delord J, Nimphius C, Patureau FW, Glorius F. Chem.–Asian J. 2012; in press; DOI: 10.1002/asia.201101018
• 7f Rakshit S, Grohmann C, Besset T, Glorius F. J. Am. Chem. Soc. 2011; 133: 2350
• 8a Huestis MP, Chan L, Stuart DR, Fagnou K. Angew. Chem. 2011; 123: 1374
• 8b Rakshit S, Patureau FW, Glorius F. J. Am. Chem. Soc. 2010; 132: 9585
• 8c Stuart DR, Bertrand-Laperle MG, Burgess KM. N, Fagnou K. J. Am. Chem. Soc. 2008; 130: 16474
• 9a Du Y, Hyster TK, Rovis T. Chem. Commun. 2011; 47: 12074
• 9b Hyster TK, Rovis T. J. Am. Chem. Soc. 2010; 132: 10565
• 9c Hyster TK, Rovis T. Chem. Sci. 2011; 2: 1606
• 10a Song G, Chen D, Pan C.-L, Crabtree RH, Li X. J. Org. Chem. 2010; 75: 7487
• 10b Song G, Gong X, Li X. J. Org. Chem. 2011; 76: 7583
• 10c Su Y, Zhao M, Han K, Song G, Li X. Org. Lett. 2010; 12: 5462
• 10d Wang F, Song G, Du Z, Li X. J. Org. Chem. 2011; 76: 2926
• 10e Wang F, Song G, Li X. Org. Lett. 2010; 12: 5430
• 10f Wei X, Zhao M, Du Z, Li X. Org. Lett. 2011; 13: 4636
• 11 Li X, Gong X, Zhao M, Song G, Deng J, Li X. Org. Lett. 2011; 13: 5808
• 12 Kim BS, Jang C, Lee DJ, Youn SW. Chem.–Asian J. 2010; 5: 2336
• 13 Typical Procedure of Olefination Reactions A pressure tube was charged with Ag₂CO₃ (297 mg, 1.08 mmol, 2 equiv), [RhCp^*Cl₂]₂ (13.3 mg, 0.0216 mmol, 4 mol%), and 1a (100 mg, 0.54 mmol, 1 equiv). After purging with nitrogen, MeCN (3 mL) and 2c (138 mg, 1.08 mmol, 2 equiv) were added. The tube was sealed, and the mixture was stirred at 115 °C for 16 h, followed by diluting with CH₂Cl₂ and filtration through Celite. All volatiles were removed under reduced pressure. The purification was performed by flash column chromatography on silica gel using EtOAc in PE to give 3c (yield 89%). Spectral Data Compound 3c (major isomer): ¹H NMR (500 MHz, CDCl₃): δ = 7.66 (d, J = 8.2 Hz, 1 H), 7.58–7.47 (m, 1 H), 7.42 (s, 2 H), 7.39–7.32 (m, 1 H), 6.97 (s, 1 H), 6.03 (s, 1 H), 3.25 (d, J = 14.8 Hz, 1 H), 2.99–2.85 (m, 1 H), 2.54 (s, 3 H), 1.19 (s, 9 H). ¹³C NMR (126 MHz, CDCl₃): δ = 169.48, 168.64, 141.86, 138.77, 131.64, 129.96, 128.59, 128.32, 123.53, 119.07, 117.65, 107.05, 80.63, 62.67, 40.33, 27.75, 25.41. ESI-HRMS: m/z calcd for [C₁₉H₂₁NO₃ + H]⁺: 312.1599; found: 312.1592. Compound 5a: ¹H NMR (500 MHz, DMSO): δ = 9.90 (s, 1 H), 8.10 (d, J = 16.0 Hz, 1 H), 7.95–7.84 (m, 2 H), 7.62 (d, J = 7.4 Hz, 2 H), 7.55–7.46 (m, 3 H), 7.40 (t, J = 7.7 Hz, 2 H), 7.33 (d, J = 7.2 Hz, 1 H), 7.27 (t, J = 7.3 Hz, 1 H), 6.75 (d, J = 16.0 Hz, 1 H), 1.82 (s, 3 H). ¹³C NMR (126 MHz, DMSO): δ = 169.37, 137.95, 135.82, 135.47, 134.54, 130.87, 129.35, 129.27, 129.16, 129.05, 128.24, 128.01, 127.91, 127.65, 126.83, 126.12, 126.04, 23.49. ESI-HRMS: m/z calcd for [C₂₀H₁₇NO + H]⁺: 288.1388; found: 288.1394. Compound 6a: ¹H NMR (500 MHz, CDCl₃): δ = 8.01 (d, J = 7.1 Hz, 1 H), 7.68 (d, J = 8.2 Hz, 1 H), 7.53–7.43 (m, 3 H), 7.40–7.16 (m, 6 H), 6.81 (d, J = 15.8 Hz, 1 H), 6.22 (dd, J = 15.8, 8.3 Hz, 1 H), 6.06 (d, J = 8.2 Hz, 1 H), 2.40 (s, 3 H). ¹³C NMR (125 MHz, CDCl₃): δ = 169.68, 142.73, 138.26, 135.72, 132.02, 131.33, 129.60, 129.08, 128.78, 128.44, 128.09, 127.18, 126.71, 123.96, 119.33, 117.29, 110.84, 69.33, 24.43. ESI-HRMS: m/z calcd for [C₂₁H₁₇NO + H]⁺: 300.1388; found: 300.1382. Compound 3gg: ¹H NMR (500 MHz, CDCl₃): δ = 7.52 (d, J = 8.4 Hz, 1 H), 7.43–7.38 (m, 1 H), 7.29–7.24 (m, 1 H), 7.11 (dd, J = 6.9, 1.4 Hz, 1 H), 6.95 (d, J = 8.2 Hz, 1 H), 6.24 (d, J = 7.2 Hz, 1 H), 5.07 (m, 1 H), 3.72–3.59 (m, 2 H), 3.49–3.38 (m, 1 H), 3.33 (dd, 1 H), 2.38–2.29 (m, 1 H), 2.27–2.18 (m, 1 H), 1.72–1.67 (m, 2 H), 0.98 (t, J = 7.4 Hz, 3 H). ¹³C NMR (126 MHz, CDCl₃): δ = 151.86, 141.90, 132.01, 130.29, 129.90, 127.85, 122.84, 115.80, 112.05, 97.57, 65.99, 59.05, 48.06, 35.33, 20.90, 11.74. ESI-HRMS: m/z calcd for [C₁₆H₁₉NO + H]⁺: 242.1545; found: 242.1549
• 14 Tsai AS, Brasse M, Bergman RG, Ellman JA. Org. Lett. 2011; 13: 540