Citation: Di Chen, Han-Jie Mo, Ding-Ben Chen, Jian-Guo Yang. Direct C-H amination for indole synthesis from N-Ts-2-Styrylaniline derivatives catalyzed by copper salt[J]. Chinese Chemical Letters, ;2015, 26(8): 969-972. doi: 10.1016/j.cclet.2015.04.020 shu

Direct C-H amination for indole synthesis from N-Ts-2-Styrylaniline derivatives catalyzed by copper salt

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School of Pharmaceutical and Chemical Engineering, Taizhou University, Taizhou 317000, China

Corresponding author: Jian-Guo Yang,
Received Date: 7 February 2015
Available Online: 24 March 2015
Fund Project: This work was financially supported by the National Natural Science Foundation of China (Nos. 21272169, 21302135) (Nos. 21272169, 21302135) the Key Innovation Team of Science & Technology in Zhejiang Province (No. 2010R50018-10) (No. 2010R50018-10)the Key Disciplines of Applied Chemistry of Zhejiang Province, Taizhou University. (No. 08KY10)

A direct C-H amination reaction of N-Ts-2-Styrylaniline derivatives to realize the synthesis of indole derivatives was developed in the presence of copper salt. A variety of N-Ts-2-Styrylaniline derivatives were transformed into the corresponding indole products in good to excellent yield under mild conditions with the oxidation of potassium persulfate.
- C-H amination,
- N-Ts-2-Styrylaniline derivatives,
- Indole,
- Copper salt,
- Potassium persulfate
1. [1]
  [1] (a) S.W. Youn, S.J. Pastine, D. Sames, Ru(III)-catalyzed cyclization of arene-alkene substrates via intramolecular electrophilic hydroarylation, Org. Lett. 6 (2004) 581-584; (b) X.D. Zhao, E. Dimitrijević, Vy M. Dong, Palladium-catalyzed C-H bond functionalization with arylsulfonyl chlorides, J. Am. Chem. Soc. 131 (2009) 3466-3467; (c) S. Pan, J. Liu, H. Li, et al., Iron-catalyzed N-alkylation of azoles via oxidation of C-H bond adjacent to an oxygen atom, Org. Lett. 12 (2010) 1932-1935; (d) X. Wang, L. Truesdale, J.Q. Yu, Pd(II)-catalyzed ortho-trifluoromethylation of arenes using TFA as a promoter, J. Am. Chem. Soc. 132 (2010) 3648-3649; (e) P.Y. Choy, C.P. Lau, F.Y. Kwong, Palladium-catalyzed direct and regioselective C-H bond functionalization/oxidative acetoxylation of indoles, J. Org. Chem. 76 (2011) 80-84; (f) H. Xu, Y. Zhang, J. Huang, W.Z. Chen, Copper-catalyzed synthesis of N-fused heterocycles through regioselective 1,2-aminothiolation of 1,1-dibromoalkenes, Org. Lett. 12 (2010) 3704-3707.
2. [2]
  [2] For selected examples: (a) T Nishikata, A.R. Abela, S. Huang, B.H. Lipshutz, Cationic palladium(II) catalysis: C-H activation/Suzuki-Miyaura couplings at room temperature, J. Am. Chem. Soc. 132 (2010) 4978-4979; (b) A.J.A. Watson, A.C. Maxwell, J.M.J. Williams, Ruthenium-catalyzed aromatic C-H activation of benzylic alcohols via remote electronic activation, Org. Lett. 12 (2010) 3856-3859; (c) H.A. Duong, R.E. Gilligan, M.L. Cooke, M.J. Gaunt, Copper(II)-catalyzed metaselective direct arylation of a-aryl carbonyl compounds, Angew. Chem. Int. Ed. 49 (2010) 1-5; (d) C.X. Song, G.X. Cai, T.R. Farrell, Z.J. Shi, Direct functionalization of benzylic C-Hs with vinyl acetates via Fe-catalysis, Chem. Commun. (2009) 6002-6004; (e) D.J. Tang, B.X. Tang, J.H. Li, Selective synthesis of 3-aryl quinolin-2(¹H)-ones and 3-(1-arylmethylene)oxindoles involving a 2-fold arene C-H activation process, J. Org. Chem. 74 (2009) 6749-6755; (f) C. Guo, J. Song, S.W. Luo, L.Z. Gong, Enantioselective oxidative cross-coupling reaction of 3-indolylmethyl C-H bonds with 1, 3-dicarbonyls using a chiral Lewis acid-bonded nucleophile to control stereochemistry, Angew. Chem. Int. Ed. 49 (2010) 5558-5562.
3. [3]
  [3] For selected examples: (a) A Boyer, N. Isono, S. Lackner, M. Lautens, Domino rhodium(I)-catalysed reactions for the efficient synthesis of substituted benzofurans and indoles, Tetrahedron 66 (2010) 6468-6482; (b) V.A. Schmidt, E.J. Alexanian, Metal-free, aerobic dioxygenation of alkenes using hydroxamic acids, Angew. Chem. Int. Ed. 49 (2010) 1-5; (c) G. Song, D. Chen, R.H. Crabtree, X.W. Li, Rh-catalyzed oxidative coupling between primary and secondary benzamides and alkynes: synthesis of polycyclic amides, J. Org. Chem. 75 (2010) 7487-7490; (d) K. Morimoto, K. Hirano, T. Satoh, M. Miura, Rhodium-catalyzed oxidative coupling/cyclization of 2-phenylindoles with alkynes via C-H and N-H bond cleavages with air as the oxidant, Org. Lett. 12 (2010) 2068-2071; (e) C.P. Frazier, J.R. Engelking, J.R. Alaniz, Copper-catalyzed aerobic oxidation of hydroxamic acids leads to a mild and versatile acylnitroso ene reaction, J. Am. Chem. Soc. 133 (2011) 10430-10433; (f) L. Chu, X. Yue, F.L. Qing, Cu(II)-mediated methylthiolation of aryl C-H bonds with DMSO, Org. Lett. 12 (2010) 1644-1647.
4. [4]
  [4] For selected examples: (a) S Li, J. Wu, Synthesis of H-pyrazolo［5,1-a］isoquinolines via copper(II)-catalyzed oxidation of an aliphatic C-H bond of tertiary amine in air,, Org. Lett. 13 (2011) 712-715; (b) H.G. Wang, Y. Wang, D.D. Liang, Q. Zhu, Copper-catalyzed intramolecular dehydrogenative aminooxygenation: direct access to formyl-substituted aromatic N-heterocycles, Angew. Chem. Int. Ed. 50 (2011) 1-5; (c) H.G. Wang, Y. Wang, C.L. Peng, J.C. Zhang, Q. Zhu, A direct intramolecular C-H amination reaction cocatalyzed by copper(II) and iron(III) as part of an efficient route for the synthesis of pyrido［1,2-a］benzimidazoles from N-aryl-2-aminopyridines, J. Am. Chem. Soc. 132 (2010) 13217-13219; (d) S.M. Guo, B. Qian, Y.J. Xie, C.G. Xia, H.M. Huang, Copper-catalyzed oxidative amination of benzoxazoles via C-H and C-N bond activation: a new strategy for using tertiary amines as nitrogen group sources, Org. Lett. 13 (2011) 522-525.
5. [5]
  [5] (a) G.W. Gribble, Recent developments in indole ring synthesis-methodology and applications, J. Chem. Soc., Perkin Trans. 1 (2000) 1045-1075; (b) S. Hibino, T. Choshi, Simple indole alkaloids and those with a nonrearranged monoterpenoid unit, Nat. Prod. Rep. 19 (2002) 148-180.
6. [6]
  [6] (a) L.S. Hegedus, Transition metals in the synthesis and functionalization of indoles ［new synthesis methods (72)］, Angew. Chem., Int. Ed. 27 (1988) 1113-1126; (b) G. Zeni, R.C. Larock, Synthesis of heterocycles via palladium π-olefin and π-alkyne chemistry, Chem. Rev. 104 (2004) 2285-2310; (c) P. Luo, R.Y. Tang, P. Zhong, J.H. Li, Progress in the synthesis of nitrogencontaining heterocycles by in-tramolecular cyclization of alkynes, Chin. J. Org. Chem. 29 (2009) 1924-1937; (d) D.F. Taber, P.K. Tirunahari, Indole synthesis: a review and proposed classification, Tetrahedron 67 (2011) 7195-7210.
7. [7]
  [7] L.S. Hegedus, G.F. Allen, J.J. Bozell, E.L. Waterman, Palladium-assisted intramolecular amination of olefins. synthesis of nitrogen heterocycles, J. Am. Chem. Soc. 100 (1978) 5800-5807.
8. [8]
  [8] (a) P.J. Harrington, L.S. Hegedus, Palladium-catalyzed reactions in the synthesis of 3-and 4-substituted indoles. Approaches to ergot alkaloids, J. Org. Chem. 49 (1984) 2657-2662; (b) S. Cacchi, G. Fabrizi, Synthesis and functionalization of indoles through palladium-catalyzed reactions, Chem. Rev. 105 (2005) 2873-2920; (c) G. Zeni, R.C. Larock, Synthesis of heterocycles via palladium-catalyzed oxidative addition, Chem. Rev. 106 (2006) 4644-4680; (d) S.W. Youn, J.H. Bihn, B.S. Kim, Pd-catalyzed intramolecular oxidative C-H amination: synthesis of carbazoles, Org. Lett. 13 (2011) 3738-3741.
9. [9]
  [9] T.W. Liwosz, S.R. Chemler, Copper-catalyzed oxidative amination and allylic amination of alkenes, Chem. Eur. J. 19 (2013) 12771-12777.
10. [10]
  [10] S. Maity, N. Zheng, A visible-light-mediated oxidative C-N bond formation/ aromatization cascade: photocatalytic preparation of N-arylindoles, Angew. Chem. Int. Ed. 51 (2012) 9562-9566.
11. [11]
  [11] Y.H. Jang, S.W. Youn, Metal-free C-H amination for indole synthesis, Org. Lett. 16 (2014) 3720-3723.
12. [12]
  [12] (a) J.G. Yang, Z.J. Wang, F.Y. Pan, W.L. Bao, CuBr-catalyzed selective oxidation of N-azomethine: highly efficient synthesis of methine-bridged bis-indole compounds, Org. Biomol. Chem. 8 (2010) 2975-2978; (b) J.G. Yang, D. Chen, W.L. Bao, Stereo-selective synthesis of cis-alkenes/haloalkenes by reaction of diphenylmethane with ethynylbenzenes via sp3 C-H bond activation promoted by iron salts, Tetrahedron Lett. 53 (2012) 3984-3989; (c) D. Chen, F.Y. Pan, J.R. Gao, J.G. Yang, Iron catalyzed direct C(sp3)-H amination reactions of isochroman derivatives with primary arylamines under mild conditions, Synlett 24 (2013) 2085-2088.
13. [13]
  [13] Z.Y. Xie, Y.P. Cai, J.L. Jiang, Cu-catalyzed cross-dehydrogenative coupling reactions of (benzo)thiazoles with cyclic ethers, Org. Lett. 15 (2013) 4600-4603.
14. [14]
  [14] (a) J. Wang, S. Wang, J. Zhang, X.Q. Yu, ChemInform abstract: iron-mediated direct arylation with arylboronic acids through an aryl radical transfer pathway, Chem. Commun. 48 (2012) 11769-11771; (b) S.A. Shahzad, C. Vivant, T. Wirth, Selenium-mediated synthesis of biaryls through rearrangement, Org. Lett. 12 (2010) 1364-1367; (c) B.J. Stokes, S. Liu, T.G. Driver, Rh2(II)-catalyzed nitro-group migration reactions: selective synthesis of 3-nitroindoles from β-nitro styryl azides, J. Am. Chem. Soc. 133 (2011) 4702-4705.
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