Citation: Zhu Runyu, Zhai Min, Liu Shuang, Liu Xingtong, Wang Zhen, Ju Ruijun, Yu Xinhong. One-Pot Synthesis of N-Alkyl Indole from Indoline-2-carboxylic Acids and Alkyl Halides by 2, 3-Dicyano-5, 6-dichlorobenzoquinone (DDQ) Mediated Oxidative Decaboylative Aromatization[J]. Chinese Journal of Organic Chemistry, ;2020, 40(7): 2045-2050. doi: 10.6023/cjoc202001025 shu

One-Pot Synthesis of N-Alkyl Indole from Indoline-2-carboxylic Acids and Alkyl Halides by 2, 3-Dicyano-5, 6-dichlorobenzoquinone (DDQ) Mediated Oxidative Decaboylative Aromatization

Zhu Runyu ^a,† ,
Zhai Min ^a,† ,
Liu Shuang ^a ,
Liu Xingtong ^a ,
Wang Zhen ^b,, ,
Ju Ruijun ^c,, ,
Yu Xinhong ^a,,

a.
Engineering Research Center of Pharmaceutical Process Chemistry, Ministry of Education, Shanghai Key Laboratory of New Drug Design, State Key Laboratory of Bioengineering Reactors, School of Pharmacy, East China University of Science & Technology, Shanghai 200237
b.
School of Pharmacy, Linyi University, Linyi, Shandong 276000
c.
College of Chemical Engineering, Beijing Institute of Petrochemical Technology, Beijing 102617

Corresponding author: Wang Zhen, wangzhen@lyu.edu.cn Ju Ruijun, juruijun@bipt.edu.cn Yu Xinhong, xhyu@ecust.edu.cn
Received Date: 17 January 2020
Revised Date: 21 March 2020
Available Online: 23 April 2020
Fund Project: the Science and Technology Commission of Shanghai Municipality 12431900902the National Science Foundation of China (NSFC) 21476078the National Science Foundation of China (NSFC) 81703453Project supported by the National Science Foundation of China (NSFC) (Nos. 21476078, 81703453) and the Science and Technology Commission of Shanghai Municipality (No. 12431900902)

Figures(3)

Synthesis of N-alkyl indoles via 2, 3-dicyano-5, 6-dichlorobenzoquinone (DDQ) mediated intramolecular oxidative decarboxylative aromatization of N-alkylindoline-2-carboxylic acids is reported. The good compatibility of this process leads to the development of a mild and metal-free one-pot synthesis of N-alkyl indoles from alkyl halides and indoline carboxylic acid. The one-pot three-component synthesis of 1, 4-bis((1H-indol-1-yl)methyl)benzene is also disclosed in satisfied yields.
- aromatization,
- 2, 3-dicyano-5, 6-dichlorobenzoquinone (DDQ),
- decarboxylation,
- N-alkyl indoles,
- oxidation
1. [1]
  Selected reviews on the synthesis of indoles: (a) Humphrey, G. R.; Kuethe, J. T. Chem. Rev. 2006, 106, 2875.
  (b) Gribble, G. W. J. Chem. Soc., Perkin Trans. 1 2000, 1045.
  (c) Cacchi, S.; Fabrizi, G. Chem. Rev. 2005, 105, 2873.
  (d) Lounasmaa, M.; Tolvanen, A. Nat. Prod. Rep. 2000, 17, 175.
2. [2]
  (a) Evans, B. E.; Rittle, K. E.; Bock, M. G.; DiPardo, R. M.; Freidinger, R. M.; Whitter, W. L.; Lundell, G. F.; Veber, D. F.; Anderson, P. S. J. Med. Chem. 1988, 31, 2235.
  (b) Nicolaou, K. C.; Pfefferkorn, J. A.; Roecker, A. J.; Cao, G. Q.; Barluenga, S.; Mitchell, H. J. J. Am. Chem. Soc. 2000, 122, 9939.
3. [3]
  (a) Sundberg, R. J. The Chemistry of Indoles, Academic Press, New York, 1970.
  (b) Sundberg, R. J. Indoles, Academic Press, London, UK, 1966.
  (c) Sexton, J. E. Indoles, Wiley, New York, 1983.
4. [4]
  (a) Barbero, N.; San Martin, R.; Domínguez, E. Tetrahedron Lett. 2009, 50, 2129.
  (b) Knaack, M.; Emig, P.; Bats, J. W. Eur. J. Org. Chem. 2001, 3843.
5. [5]
  (a) Willis, M. C.; Brace, G. N.; Findla. T. J. K.; Holmes, I. P. Adv. Synth. Catal. 2006, 348, 851.
  (b) Willis, M. C.; Brace, G. N.; Holmes, I. P. Angew. Chem. 2005, 117, 407.
6. [6]
  Barluenga, J.; Jiménez-Aquino, A.; Aznar. F.; Valdés, C. J. Am. Chem. Soc. 2009, 131, 4031. doi: 10.1021/ja808652a
7. [7]
  Barluenga, J.; Jiménez-Aquino, A. Angew. Chem., Int. Ed. 2007, 46, 1529. doi: 10.1002/anie.200604407
8. [8]
  Bähn, S.; Imm, S.; Mevius, K..; Neubert, L.; Tillack, A.; Williams, J. M. J.; Beller, M. Chem.-Eur. J. 2010, 16, 3590. doi: 10.1002/chem.200903144
9. [9]
  For reviews on the Shvo catalyst, see: (a) Samec, J. S. M. Backvall, J. E. e-EROS Encycl. Reagents Org. Synth. 2009, 7, 5557.
  (b) Comas-Vives, A.; Ujaque, G.; Lledos, A. J. Mol. Struct.: THEOCHEM 2009, 903, 123.
  (c) Karvembu, R.; Prabhakaran, R.; Natarajan, K. Coord. Chem. Rev. 2005, 249, 911.
  (d) Prabhakaran, R. Synlett 2004, 2048.
10. [10]
  (a) Mays, M. J.; Morris, M. J.; Raithby, P. R.; Shvo, Y.; Czarkie, D. Organometallics 1989, 8, 1162.
  (b) Shvo, Y.; Czarkie, D. J. Am. Chem. Soc. 1986, 108, 7400.
  (c) Shvo, Y.; Thomasand, D. W.; Laine, R. M. J. Chem. Soc., Chem. Commun. 1980, 249, 753.
11. [11]
  Hara, T.; Mori, K.; Mizugaki, T.; Ebitani, K.; Kaneda, K. Tetrahedron Lett. 2003, 44, 6207. doi: 10.1016/S0040-4039(03)01550-8
12. [12]
  Mao, H.; Wang, S.; Yu, P.; Lv, H.; Xu, R. S.; Pan, Y. J. J. Org. Chem. 2011, 76, 1167.
13. [13]
  Reddy, K. H. V.; Satish, G.; Ramesh, K.; Karnakar, K.; Nageswar, Y. V. D. Tetrahedron Lett. 2012, 53, 3061. doi: 10.1016/j.tetlet.2012.04.012
14. [14]
  Wang, J.; Shen, Q.; Zhang, J.; Song, G. Tetrahedron Lett. 2015, 56, 2913. doi: 10.1016/j.tetlet.2015.04.074
15. [15]
  (a) Tang, M.; Tong, L. F.; Ju, L.; Zhai, W. W.; Hu, Y.; Yu, X. H. Org. Lett. 2015, 17, 5180.
  (b) Zou, Z. Q.; Deng, Z. J.; Yu, X. H.; Zhang, M. M.; Zhao, S. H.; Luo, T.; Yin, X.; Xu, H.; Wang, W. Sci. China, Chem. 2012, 55, 43.
16. [16]
  For the pioneering work about CuBr-mediated intramolecular oxidative decarboxylation of α-tertiary amino acids, see: Bi, H. P.; Zhao, L.; Liang, Y. M.; Li. C. J. Angew. Chem., Int. Ed. 2009, 48, 792.
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