G
Synthesis
Z.-Z. Jiang et al.
Paper
(
R)-6-Chloro-2-(4-methoxyphenyl)-1,2,3,4-tetrahydroquinoline
(2) (a) Yasui, S.; Fujii, M.; Kawano, C.; Nishimura, Y.; Ohno, A. Tetra-
hedron Lett. 1991, 32, 5601. (b) Yasui, S.; Fujii, M.; Kawano, C.;
Nishimura, Y.; Shioji, K.; Ohno, A. J. Chem. Soc., Perkin Trans. 2
(4)
A solution of compound 3c (18.6 mg, 0.05 mmol) in EtOAc (2 mL) con-
taining 10 wt% Pd/C (5 mg) was stirred under a H2 atmosphere at rt
for 2 h. Upon completion of the reaction, the mixture was filtered
over Celite and rinsed with EtOAc. The filtrate was evaporated and the
crude product was transferred to a flame-dried, argon-flushed 100
mL two-neck round-bottom flask. 2,6-Lutidine (6 L, 0.05 mmol) and
CH Cl (2 mL) were added. Next, TMSOTf (44.45 mg, 0.2 mmol) was
added dropwise to the stirred mixture at 0 °C. The reaction was
stirred at rt until full conversion (monitored by TLC, PE/EtOAc = 20:1).
The solvent was removed under vacuum and the residue purified by
1994, 177.
(
3) (a) Correia, C. R. D.; Oliveira, C. C.; Salles, A. G. Jr.; Santos, E. A. F.
Tetrahedron Lett. 2012, 53, 3325. (b) Oliveira, C. C.; Angnes, R. A.;
Correia, C. R. D. J. Org. Chem. 2013, 78, 4373. (c) de Azambuja, F.;
Carmona, R. C.; Chorro, T. H. D.; Heerdt, G.; Correia, C. R. D.
Chem. Eur. J. 2016, 22, 11205. (d) de Oliveira Silva, J.; Angnes, R.
A.; Menezes da Silva, V. H.; Servilha, B. M.; Adeel, M.; Braga, A.
A. C.; Aponick, A.; Correia, C. R. D. J. Org. Chem. 2016, 81, 2010.
2
2
(e) Kattela, S.; Heerdt, G.; Correia, C. R. D. Adv. Synth. Catal. 2017,
11
359, 260. (f) Frota, C.; Polo, E. C.; Esteves, H.; Correia, C. R. D.
J. Org. Chem. 2018, 83, 2198. (g) Silva, A. R.; Polo, E. C.; Martins,
N. C.; Correia, C. R. D. Adv. Synth. Catal. 2018, 360, 346.
flash column chromatography over silica gel to yield the product 4.
29
Yield: 10.2 mg (78%); yellow oil; ee: 78%; [] = 15.9 (c 0.51, EtOAc)
D
11
20
[
(S)-4: Lit. 98% ee; []D = –35.1 (c 0.97, EtOAc)].
(h) Carmona, R. C.; Köster, O. D.; Correia, C. R. D. Angew. Chem.
HPLC (Chiralcel AD-H; 4.6 mm × 250 mm; hexane/i-propanol = 96:4;
1
Int. Ed. 2018, 57, 12067.
.0 mL/min, 214 nm): t (major) = 12.62 min, t (minor) = 25.07 min.
R
R
(4) (a) Werner, E. W.; Mei, T.-S.; Burckle, A. J.; Sigman, M. S. Science
2012, 338, 1455. (b) Mei, T.-S.; Patel, H. H.; Sigman, M. S. Nature
2014, 508, 340. (c) Dang, Y.; Qu, S.; Wang, Z.-X.; Wang, X. J. Am.
Chem. Soc. 2014, 136, 986. (d) Xu, L.; Hilton, M. J.; Zhang, X.;
Norrby, P.-O.; Wu, Y.-D.; Sigman, M. S.; Wiest, O. J. Am. Chem.
Soc. 2014, 136, 1960.
1
H NMR (400 MHz, CDCl ): = 7.29 (d, J = 8.4 Hz, 2 H), 6.95 (d, J = 11.6
3
Hz, 2 H), 6.89 (d, J = 8.4 Hz, 2 H), 6.44 (d, J = 8.3 Hz, 1 H), 4.36 (dd, J =
9
Hz, 1 H), 2.70 (dt, J = 16.5, 4.4 Hz, 1 H), 2.13–2.00 (m, 1 H), 1.93 (ddd,
J = 18.1, 12.0, 5.1 Hz, 1 H).
.3, 2.6 Hz, 1 H), 4.01 (s, 1 H), 3.82 (s, 3 H), 2.88 (ddd, J = 16.2, 10.7, 5.4
1
3
(5) (a) Avila, C. M.; Patel, J. S.; Reddi, Y.; Saito, M.; Nelson, H. M.;
Shunatona, H. P.; Sigman, M. S.; Sunoj, R. B.; Toste, F. D. Angew.
Chem. Int. Ed. 2017, 56, 5806. (b) Reddi, Y.; Tsai, C.-C.; Avila, C.
M.; Toste, F. D.; Sunoj, R. B. J. Am. Chem. Soc. 2019, 141, 998.
C NMR (101 MHz, CDCl ): = 158.99, 143.34, 136.39, 128.83,
3
1
2
27.57, 126.63, 122.36, 121.36, 114.88, 113.93, 55.57, 55.33, 30.59,
6.33.
MS (ESI): m/z = 274.1 [M + H]+.
(
6) (a) Tu, T.; Deng, W. P.; Hou, X. L.; Dai, L. X.; Dong, X. C. Chem.
Eur. J. 2003, 9, 3073. (b) Hou, X. L.; Dong, D. X.; Yuan, K. Tetrahe-
dron: Asymmetry 2004, 15, 2189. (c) Wu, W.-Q.; Peng, Q.; Dong,
D.-X.; Hou, X.-L.; Wu, Y.-D. J. Am. Chem. Soc. 2008, 130, 9717.
Funding Information
(
(
d) Ding, C.-H.; Hou, X.-L. Bull. Chem. Soc. Jpn. 2010, 83, 992.
e) Li, H.; Ding, C.-H.; Xu, B.; Hou, X.-L. Acta Chim. Sinica 2014,
We acknowledge financial support from the National Natural Science
Foundation of China (NSFC) (grants 21772215, 21532010 and
2
Academy of Sciences (grant XDB20030100), the NSFC and the Re-
search Grants Council of Hong Kong Joint Research Scheme (grant
2
72, 765. (f) Li, H.; Wan, S.-L.; Ding, C.-H.; Xu, B.; Hou, X.-L. RSC
1472214), the Strategic Priority Research Program of the Chinese
Adv. 2015, 5, 75411. (g) Li, H.; Gao, A.; Liu, X.-Y.; Ding, C.-H.; Xu,
B.; Hou, X.-L. Synthesis 2017, 49, 159.
(7) Jiang, Z.-Z.; Gao, A.; Li, H.; Chen, D.; Ding, C.-H.; Xu, B.; Hou, X.-L.
Chem. Asian J. 2017, 12, 3119.
1361162001), the Chinese Academy of Sciences, the Technology
Commission of Shanghai Municipality and the Croucher Foundation
of Hong Kong.
(8) (a) Rokotoson, J. H.; Fabre, N.; Jacquemond-Collet, I.;
Hannedouche, S.; Fabre, N.; Fouraste, I.; Moulis, C. Planta Med.
N
ati
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1998, 64, 762. (b) Sridharan, V.; Suryavanshi, P. A.; Menendez, J.
C. Chem. Rev. 2011, 111, 7157. (c) Chung, P. Y.; Bian, Z. X.; Pun,
H. Y.; Chan, D.; Chan, A. S. C.; Chui, C. H.; Tang, J. C. O.; Lam, K. H.
Future Med. Chem. 2015, 7, 947.
Supporting Information
Supporting information for this article is available online at
https://doi.org/10.1055/s-0037-1610712.
(
9) For selected examples of synthetic methods to access optically
active 2-substituted hydroquinolines, see: (a) Wang, W.-B.; Lu,
S.-M.; Yang, P.-Y.; Han, X.-W.; Zhou, Y.-G. J. Am. Chem. Soc. 2003,
S
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o
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orti
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1
25, 10536. (b) Rueping, M.; Antonchick, A. R.; Theissmann, T.
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©
Georg Thieme Verlag Stuttgart · New York — Synthesis 2019, 51, A–H