Citation: Shi Zeyu, Xiao Qiong, Yin Dali. Synthesis of tetrahydroisoquinolines through TiCl₄-mediated cyclization and Et₃SiH reduction[J]. Chinese Chemical Letters, ;2020, 31(3): 729-732. doi: 10.1016/j.cclet.2019.09.023 shu

Synthesis of tetrahydroisoquinolines through TiCl₄-mediated cyclization and Et₃SiH reduction

Shi Zeyu ^a ,
Xiao Qiong ^a,b,*, ,
Yin Dali ^a,b

a.
State Key Laboratory of Bioactive Substances and Functions of Natural Medicines, Institute of Materia Medica, Peking Union Medical College and Chinese Academy of Medical Sciences, Beijing 100050, China
b.
Department of Medicinal Chemistry, Beijing Key Laboratory of Active Substances Discovery and Drugability Evaluation, Institute of Materia Medica, Peking Union Medical College and Chinese Academy of Medical Sciences, Beijing 100050, China

xiaoqiong@imm.ac.cn

Received Date: 27 July 2019
Revised Date: 4 September 2019
Accepted Date: 11 September 2019
Available Online: 12 September 2019

Figures(3)

A versatile and efficient telescoped reaction sequence for the synthesis of tetrahydroisoquinolines (THIQs) is reported that uses TiCl₄ to promote cyclization of a benzylaminoacetal derivative and Et₃SiH for reduction of the intermediate 4-hydroxy-THIQ. This method is complimentary to the classical Pomeranz-Fritsch and related reactions since it tolerates electron-withdrawing substituents and allows access to 8-substituted THIQs.
- Tetrahydroisoquinoline,
- TiCl₄,
- Cyclization,
- Et₃SiH,
- Telescoped reaction
1. [1]
  (a) J.D. Scott, R.M. Williams, Chem. Rev. 102 (2002) 1669-1730;
  (b) Y. Kashiwasa, A. Aoshima, Y. Ikeshiro, et al., Bioorg. Med. Chem. 13 (2005) 443-448.
2. [2]
  (a) A.D. Pechulis, J.P. Beck, M.A. Curry, et al., Bioorg. Med. Chem. Lett. 22 (2012) 7219-7222;
  (b) W.O. Shekim, A. Masterson, D.P. Cantwell, et al., J. Nerv. Ment. Dis. 177 (1989) 296-299;
  (c) E. Zara-Kaczian, L. Gyorgy, G. Deak, et al., J. Med. Chem. 29 (1986) 1189-1195.
3. [3]
  R.W. Freudenmann, F. Oxler, S. Bernschneider-Reif, Addiction 101 (2006) 1241-1245. doi: 10.1111/j.1360-0443.2006.01511.x
4. [4]
  G.H. Al-Khateeb, T.I. Al-Jeboori, K.A. Al-Janabi, Chemotherapy 23 (1977) 267-275.
5. [5]
  E.J. Corey, D.Y. Gin, R.S. Kania, J. Am. Chem. Soc. 118 (1996) 9202-9203. doi: 10.1021/ja962480t
6. [6]
  (a) A. Pictet, T. Spengler, Ber. Dtsch. Chem. Ges. 44 (1911) 2030-2036;
  (b) S.W. Youn, J. Org. Chem. 71 (2006) 2521-2523.
7. [7]
  R. Quevedo, E. Baquero, M. Rodriguez, Tetrahedron Lett. 51 (2010) 1774-1778. doi: 10.1016/j.tetlet.2010.01.115
8. [8]
  X.C. Liu, K. Sun, X.L. Chen, et al., Adv. Synth. Catal. 361 (2019) 3712-3717. doi: 10.1002/adsc.201900544
9. [9]
  K. Sun, Y.F. Si, X.L. Chen, et al., Adv. Synth. Catal. 361 (2019) 4483-4488. doi: 10.1002/adsc.201900691
10. [10]
  (a) A.J. Birch, A.H. Jackson, P.V.R. Shannon, J. Chem. Soc. Perkin Trans. 1 (1974) 2185-2190;
  (b) D.L. Boger, C.E. Brotherton, M.D. Kelley, Tetrahedron 37 (1981) 3977-3980.
11. [11]
  M.J.E. Hewlins, R. Salter, Synth. Stuttg. (2007) 2157-2163.
12. [12]
  S. Bhattacharyya, J. Org. Chem. 63 (1998) 7101-7102. doi: 10.1021/jo980685+
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2. [2]
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Synthesis of tetrahydroisoquinolines through TiCl4-mediated cyclization and Et3SiH reduction

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通讯作者: 陈斌, bchen63@163.com

Synthesis of tetrahydroisoquinolines through TiCl₄-mediated cyclization and Et₃SiH reduction