L. Cheng et al. / Tetrahedron Letters 53 (2012) 4004–4007
4007
13. The reaction of C-7 lithiated indoline with aldehydes gave the cyclization
lactone products, see Ref. 8.
Acknowledgments
14. Typical procedure:
indoline 1a (44 mg, 0.2 mmol) in anhydrous Et2O (2 mL) and TMEDA (40
0.26 mmol) under N2. The resulting solution was cooled to ꢀ78 °C, s-BuLi
(185 L of a 1.3 M solution in cyclohexane/hexane 92/8, 0.24 mmol) was added
A
5 mL round-bottomed flask was charged with N-Boc
We thank the National Natural Science Foundation of China,
lL,
Ministry
of
Science
and
Technology
(973
Program
l
2011CB808600) and the Chinese Academy of Sciences for financial
support. Liang Cheng gratefully acknowledges Ms. Juan Lv (Bruker
BioSpin AG Ltd) for the operation of NOESY experiments.
dropwise via syringe. The mixture was stirred for 1 hour at ꢀ78 °C, and a
solution of N-Ts aldimine 2a (52 mg, 0.2 mmol) in Et2O was added. After
warming to room temperature, the resulting mixture was quenched with
saturated NH4Cl, and the aqueous mixture was extracted with CH2Cl2. The
organic extracts were combined, dried over anhydrous Na2SO4, filtered, and
evaporated. The crude residue was purified by chromatography on silica gel
(eluting with 20% ethyl acetate in petroleum ether) to give the product N-Ts-
(1-Boc-indolin-7-yl)-phenylmethaneamine 3a (72 mg, 75% yield) as a pale
yellow solid. Mp 168–169 °C. 1H NMR (300 MHz, CDCl3) d 1.32 (s, 9H), 2.30 (s,
3H), 2.68–2.78 (m, 2H), 3.46–3.50 (m, 1H), 3.64–3.68 (m, 1H), 6.08–6.13 (m,
2H), 6.81–6.86 (t, 2H, J = 7.5 Hz), 6.95–7.20 (m, 10H), 7.62–7.65 (m, 2H,
J = 8.2 Hz); 13C NMR (75 MHz, CDCl3) d 21.5, 28.3, 29.3, 50.6, 58.5, 80.9, 124.0,
124.5, 126.9, 127.1, 127.3, 127.9, 128.6, 129.2, 129.3, 130.5, 135.5, 140.2, 140.4,
Supplementary data
Supplementary data associated with this article can be found,
C
27H30N2O4S [M+Na]+ 501.1818.
References and notes
142.7, 153.6. HRMS (ESI) m/z Calcd for:
Found: 501.1817.
15. CCDC 736018, 736019 contain the supplementary crystallographic data for this
The Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2
1EZ, UK; fax: +44 1223 336033.
16. (a) Meyers, A. I.; Hoeve, W. T. J. Am. Chem. Soc. 1980, 102, 7125; (b) Meyers, A.
I.; Hellring, S.; Hoeve, W. T. Tetrahedron Lett. 1981, 22, 5115.
17. (a) Wu, Y.-H.; Lobeck, W. G., Jr.; Kissel, J. W. J. Med. Chem. 1970, 13, 975; (b) Wu,
Y.-H.; Lobeck, W. G., Jr.; Ryan, R. D. J. Med. Chem. 1972, 15, 529.
1. Cordell, G. A. The Alkaloids: Chemistry and Biology; Academic Press: San Diego,
1998. Vol. 50.
2. (a) Glamkowski, E. J.; Fortunato, J. M.; Geyer, H. M. J. Med. Chem. 1980, 23, 1380;
(b) Hester, J. B., Jr.; Rudzik, A. D.; Veldkamp, W. J. Med. Chem. 1970, 13, 827.
3. (a) Shibata, M.; Ito, S.; Sakai, J.; Hayashi, S. Eur. Pat. Appl. 1994, EP 587110 A2
19940316.; (b) Corey, E. J.; McCaully, R. J.; Sachdev, H. S. J. Am. Chem. Soc. 1970,
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Top. Heterocycl. Chem. 2010, 26, 141.
18. Typical procedure:
indoline 1b (40 mg, 0.2 mmol) in anhydrous THF (2 mL) under N2. The
resulting solution was cooled to ꢀ78 °C, t-BuLi (160 L of a 1.5 M solution in
A 5 mL round-bottomed flask was charged with N-Tbf
l
pentane, 0.24 mmol) was added dropwise via syringe. The mixture was stirred
at ꢀ78 °C for 5 min, then at ꢀ40 °C for 40 min, and recooled to ꢀ78 °C,
followed by the addition of THF solution of N-Ts aldimine 2a (52 mg,
0.2 mmol). After warming to room temperature, the resulting mixture was
quenched with saturated NH4Cl, and the aqueous mixture was extracted with
CH2Cl2. The organic extracts were combined, dried over anhydrous Na2SO4,
filtered, and evaporated. The crude residue was purified by chromatography on
silica gel (eluting with 20% ethyl acetate in petroleum ether) to give the
product N-Ts-(1-Tbf-indolin-2-yl)phenylmethaneamine 5b (77 mg, 84% yield)
as a white solid. Mp 203–205 °C. 1H NMR (300 MHz, CDCl3) d 1.35 (s, 9H), 2.32
(s, 3H), 2.52–2.56 (m, 1H), 2.90–2.96 (m, 1H), 4.21–4.24 (d, 1H, J = 6.6 Hz),
4.75–4.80 (m, 1H), 6.57–6.58 (d, 1H, J = 7.5 Hz), 6.87–6.90 (m, 2H), 6.99–7.11
(m, 2H), 7.21–7.28 (m, 5H), 7.38–7.40 (m, 2H), 7.84 (s, 1H); 13C NMR (75 MHz,
CDCl3) d 21.3, 30.8, 30.9, 32.3, 54.2, 63.7, 63.8, 109.3, 122.4, 125.3, 126.7, 127.4,
127.6, 128.2, 128.38, 128.44, 128.77, 128.85, 138.7, 139.5, 141.9, 144.0, 147.6.
HRMS (EI) m/z Calcd for: C27H31N3O2S [M]+ 461.2137. Found: 461.2144.
6. Meyers, A. I.; Hellring, S. Tetrahedron Lett. 1981, 22, 5119.
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I.; Kürti, K.; Davulcu, A. H.; Cho, Y. S.; Ohmoto, K. J. Org. Chem. 2007, 72, 4611;
(e) Leonori, D.; Coldham, I. Adv. Synth. Catal. 2009, 351, 2619.
8. Iwao, M.; Kuraishi, T. Heterocycles 1992, 34, 1031.
9. For examples, see: Gross, K. M. B.; Jun, Y. M.; Beak, P. J. Org. Chem. 1997, 62,
7679.
10. For some examples, see: (a) Wee, A. G. H.; Solbodian, J. J. Org. Chem. 1996, 61,
2897; (b) Lakatosh, S. A.; Luzikov, Y. N.; Preobrazhenskaya, M. N. Org. Biomol.
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Meijere, A. Chem. Eur. J. 2004, 10, 785.
11. For the synthesis of 3-indolinyl methanamines, see: (a) Ahlbrecht, H.; Schmitt,
C. Synthesis 1994, 983; (b) Ahlbrecht, H.; Kornetzky, D.; Purder, T.; Katritzky, A.
R.; Ghiviriga, I.; Levell, J. Synthesis 1997, 171.
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Cheng, L.; Liu, L.; Jia, H.; Wang, D.; Chen, Y.-J. J. Org. Chem. 2009, 74, 4650; (d)
Zhang, T.; Cheng, L.; Liu, L.; Wang, D.; Chen, Y.-J. Tetrahedron: Asymmetry 2010,
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19. For
a
recent example of bisoxazoline and (ꢀ)-sparteine mediated
enantioselective addition of organolithium to imines, see: Denmark, S. E.;
Nakajima, N.; Stiff, C. M.; Nicaise, O. J.-C.; Kranz, M. Adv. Synth. Catal. 2008, 350,
1023.
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