Aerobic Photooxidative Carbon–Carbon Bond Formation Between Tertiary Amines and Carbon Nucleophiles Using 2-Chloroanthra-9,10-quinone

Abstract

Carbon–carbon bonds were formed between tertiary amines and carbon nucleophiles such as nitroalkanes, ketones, trimethylsilyl cyanide, or indole under aerobic photooxidative conditions by using 2-chloroanthra-9,10-quinone as an organocatalyst. This reaction uses harmless visible-light irradiation with molecular oxygen as the terminal oxidant.

Key words

carbon–carbon bond formation - organocatalysis - photooxidation - amines

• References and Notes


For reviews on cross-dehydrogenative coupling, see:
• 1a Yeung CS, Dong VM. Chem. Rev. 2011; 111: 1215
• 1b Klussmann M, Sureshkumar D. Synthesis 2011; 353
• 1c Li C.-J. Acc. Chem. Res. 2009; 42: 335
• 1d Murahashi S.-I, Zhang D. Chem. Soc. Rev. 2008; 37: 1490
• 2a Murahashi S.-I, Nakae T, Terai H, Komiya N. J. Am. Chem. Soc. 2008; 130: 11005
• 2b Murahashi S.-I, Komiya N, Terai H. Angew. Chem. Int. Ed. 2005; 44: 6931
• 2c Murahashi S.-I, Komiya N, Terai H, Nakae T. J. Am. Chem. Soc. 2003; 125: 15312
• 3a Baslé O, Li C.-J. Chem. Commun. 2009; 4124
• 3b Baslé O, Li C.-J. Green Chem. 2007; 9: 1047
• 3c Li Z, Li C.-J. J. Am. Chem. Soc. 2005; 127: 6968
• 3d Li Z, Li C.-J. J. Am. Chem. Soc. 2005; 127: 3672
• 3e Li Z, Li C.-J. Org. Lett. 2004; 6: 4997
• 3f Li Z, Li C.-J. J. Am. Chem. Soc. 2004; 126: 11810
• 4a Ghobrial M, Harhammer K, Mihovilovic MD, Schnürch M. Chem. Commun. 2010; 46: 8836
• 4b Liu P, Zhou C.-Y, Xiang S, Che C.-M. Chem. Commun. 2010; 46: 2739
• 4c Zeng T, Song G, Moores A, Li C.-J. Synlett 2010; 2002
• 4d Han W, Ofial AR. Chem. Commun. 2009; 6023
• 4e Rao Volla CM, Vogel P. Org. Lett. 2009; 11: 1701
• 4f Chiavarino B, Cipollini R, Crestoni ME, Fornarini S, Lanucara F, Lapi A. J. Am. Chem. Soc. 2008; 130: 3208
• 5a Alagiri K, Kumara GS. R, Prabhu KR. Chem. Commun. 2011; 47: 11787
• 5b Sud A, Sureshkumar D, Klussmann M. Chem. Commun. 2009; 3169
• 6 Catino AJ, Nichols JM, Nettles BJ, Doyle MP. J. Am. Chem. Soc. 2006; 128: 5648
• 7 Xie J, Li H, Zhou J, Cheng Y, Zhu C. Angew. Chem. Int. Ed. 2012; 51: 1252
• 8 Shu X.-Z, Yang Y.-F, Xia X.-F, Ji K.-G, Liu X.-Y, Liang YM. Org. Biomol. Chem. 2010; 8: 4077
• 9 Shu X.-Z, Xia X.-F, Yang Y.-F, Ji K.-G, Liu X.-Y, Liang Y.-M. J. Org. Chem. 2009; 74: 7464
• 10 Su W, Yu J, Li Z, Jiang Z. J. Org. Chem. 2011; 76: 9144
• 11 Allen JM, Lambert TH. J. Am. Chem. Soc. 2011; 133: 1260

For recent reports, see:
• 12a Neel AJ, Hehn JP, Tripet PF, Toste FD. J. Am. Chem. Soc. 2013; 135: 14044
• 12b Zhang G, Ma Y, Wang S, Konga W, Wang R. Chem. Sci. 2013; 4: 2645
• 12c Zhang G, Ma Y, Wang S, Zhang Y, Wang R. J. Am. Chem. Soc. 2012; 134: 12334
• 12d Zhang J, Tiwari B, Xing C, Chen X, Chi YR. Angew. Chem. Int. Ed. 2012; 51: 3649
• 13a Nobuta T, Tada N, Fujiya A, Kariya A, Miura T, Itoh A. Org. Lett. 2013; 15: 574
• 13b Nobuta T, Fujiya A, Yamaguchi T, Tada N, Miura T, Itoh A. RSC Adv. 2013; 3: 10189
• 14 Modern Oxidation Methods . Bäckvall J.-E. Wiley-VCH; Weinheim: 2010. 2nd ed.
• 15 Condie AG, González-Gómez JC, Stephenson CR. J. J. Am. Chem. Soc. 2010; 132: 1464
• 16a Freeman DB, Furst L, Condie AG, Stephenson CR. J. Org. Lett. 2012; 14: 94
• 16b Rueping M, Vila C, Koenigs RM, Poscharny K, Fabry DC. Chem. Commun. 2011; 47: 2360
• 17a Hari DP, König B. Org. Lett. 2011; 13: 3852
• 17b Liu Q, Li Y.-N, Zhang Y.-N, Chen B, Tung C.-H, Wu L.-Z. Chem. Eur. J. 2012; 18: 620
• 18a Pan Y, Kee CW, Chen L, Tan C.-H. Green Chem. 2011; 13: 2682
• 18b Rueping M, Vila C, Bootwicha T. ACS Catal. 2013; 3: 1676
• 19 1-(Nitromethyl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline (3aa); Typical Procedure A solution of 2-phenyl-1,2,3,4-tetrahydroisoquinoline (1a, 0.3 mmol), 2­chloroanthra-9,10-quinone (0.021mmol), and MeNO₂ (2a, 1.5 mmol) in MeOH (3mL) in a Pyrex test tube, purged with an O₂ balloon, was stirred and externally irradiated by fluorescent lamps for 20 h. The mixture was then concentrated in vacuo. Purification of the crude product by flash chromatography [silica gel, hexane–EtOAc–Et₃N (100:10:1)] gave a yellow solid; mp 103.3–104.1 °C; 64.5 mg (80%); ¹H NMR (500 MHz, CDCl₃): δ = 7.28–7.16 (m, 5 H), 7.11 (d, J = 7.4 Hz, 1 H), 6.97 (d, J = 7.5 Hz, 2 H), 6.83 (t, J = 7.2 Hz, 1 H), 5.54 (t, J = 7.2 Hz, 1 H), 4.84 (dd, J = 11.4, 7.4 Hz, 1 H), 4.54 (dd, J = 12.0, 6.9 Hz, 1 H), 3.67–3.57 (m, 2 H), 3.10–3.03 (m, 1 H), 2.77 (dt, J = 16.1, 5.1 Hz, 1 H); ¹³C NMR (125 MHz, CDCl₃): δ = 148.4, 135.2, 132.8, 129.4, 129.1, 128.0, 126.9, 126.6, 119.4, 115.0, 78.7, 58.1, 42.0, 26.4. 1-(2-Phenyl-1,2,3,4-tetrahydroisoquinolin-1-yl)acetone (3ad)
  Colorless solid; mp 82.9–83.4 °C; 42.3 mg (53%); ¹H NMR (500 MHz, CDCl₃): δ = 7.26–7.12 (m, 6 H), 6.93 (d, J = 8.6 Hz, 2 H), 6.77 (t, J = 7.8 Hz, 1 H), 5.40 (t, J = 6.6 Hz, 1 H), 3.67–3.62 (m, 1 H), 3.55–3.50 (m, 1 H), 3.08–3.02 (m, 2 H), 2.82 (dt, J = 16.6, 4.5 Hz, 2 H), 2.07 (s, 3 H); ¹³C NMR (125 MHz, CDCl₃): δ = 207.3, 148.8, 138.2, 134.4, 129.3, 128.6, 126.8, 126.8, 126.2, 118.2, 114.7, 54.7, 50.1, 42.0, 31.1, 27.2. 2-Phenyl-1,2,3,4-tetrahydroisoquinoline-1-carbonitrile (3af)
  Colorless solid; mp 94.5–95.1 °C; 35.9 mg (51%); ¹H NMR (500 MHz, CDCl₃): δ = 7.41–7.22 (m, 6 H), 7.08 (d, J = 8.6 Hz, 2 H), 7.01 (t, J = 7.4 Hz, 1 H), 5.51 (s, 1 H), 3.79–3.75 (m, 1 H), 3.50–3.45 (m, 1 H), 3.18–3.12 (m, 1 H), 2.96 (dt, J = 16.0, 3.5 Hz, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 148.3, 134.6, 129.5, 129.3, 128.7, 127.0, 126.8, 121.8, 117.7, 117.6, 53.2, 44.1, 28.5.
• 20 Although diethyl malonate also reacted as substrate to give the corresponding product, the product could not be separated from diethyl malonate by flash chromatography. Neither acetylacetone nor ethyl acetoacetate gave a product.
• 21 N,N-Diphenylbenzylamine, N-methyl-N-phenylbenzyl-amine, 1,2,3,4-tetrahydroisoquinoline, and trioctylamine were also poor substrates
• 22 See the Supporting Information.