C. S. Cho, W. X. Ren / Tetrahedron Letters 50 (2009) 2097–2099
2099
Shim, S. C. Chem. Commun. 2004, 104; (c) Cho, C. S. J. Organomet. Chem. 2005,
690, 4094; (d) Cho, C. S.; Patel, D. B. Tetrahedron 2006, 62, 6388; (e) Cho, C. S.;
Patel, D. B. J. Mol. Catal. A: Chem. 2006, 260, 105; (f) Cho, C. S.; Kim, J. U.
Tetrahedron Lett. 2007, 48, 3775; (g) Cho, C. S.; Ren, W. X. J. Organomet. Chem.
2007, 692, 4182.
separated by thin layer chromatography (silica gel, ethyl acetate–
hexane mixture) to give isoindolin-1-ones 3.22
In summary, we have shown that 2-bromobenzaldehyde
undergoes carbonylative cyclization with aromatic and aliphatic
primary amines under carbon monoxide pressure in the presence
of a palladium catalyst to give isoindolin-1-ones in good yields.
The present reaction is a straightforward methodology for the syn-
thesis of isoindolin-1-ones from readily available starting com-
pounds. The mechanistic rationale and further elaborated
synthetic application for N-heterocycles using this protocol are
currently under investigation.
12. For our reports on palladium-catalyzed carbonylative cyclizations, see: Cho, C.
S.; Shim, H. S. Tetrahedron Lett. 2006, 47, 3835. and references cited therein.
13. For 2-bromobenzaldehydes as a useful annulation counterpart, see: (a) Larock,
R. C.; Doty, M. J. J. Org. Chem. 1993, 58,
4579; (b) Gevorgyan, V.; Quan, L. G.;
Yamamoto, Y. Tetrahedron Lett. 1999, 40, 4089; (c) Dyker, G.; Grundt, P.
Tetrahedron Lett. 1996, 37, 619; (d) Terao, Y.; Satoh, T.; Miura, M.; Nomura, M.
Tetrahedron 2000, 56, 1315.
14. Pri-Bar, I.; Buchman, O. J. Org. Chem. 1986, 51, 734.
15. Larock, R. C.; Babu, S. Tetrahedron Lett. 1987, 28, 5291.
16. Schreiner, S.; Yu, J. Y.; Vaska, L. J. Chem. Soc., Chem. Commun. 1988, 602.
17. Yu, J. Y.; Schreiner, S.; Vaska, L. Inorg. Chim. Acta 1990, 170, 145.
18. Schumacher, N.; Boisen, A.; Dahl, S.; Gokhale, A. A.; Kandoi, S.; Grabow, L. C.;
Dumesic, J. A.; Mavrikakis, M.; Chorkendorff, I. J. Catal. 2005, 229, 265.
Acknowledgment
1
19. Deuterated 3a was characterized with 13C NMR spectrum [d 50.58 (t, JC–
This work was supported by the Korea Research Foundation
Grant funded by the Korean Government (MOEHRD, Basic Research
Promotion Fund) (KRF-2008-331-C00176).
D = 21.8 Hz)] and the distribution was determined from the comparision of the
peak area of
a
clearly separated signal with benzylic signal in 1H NMR
spectrum. An excess H2O seems to reduce the product yield by imine
hydrolysis.
20. Cho, C. S.; Kim, J. U.; Choi, H.-J. J. Organomet. Chem. 2008, 693, 3677.
21. A reviewer suggested that the transformation of 7 to 3 may also involve a
hydridopalladium(II) 8 formation by the action of CO (on coordination sphere)
and H2O without forming H2.
22. Selected spectroscopic data. Compound 3a: Solid (hexane–chloroform); mp
162–163 °C; (lit.23 163–163.5 °C); 1H NMR (400 MHz, CDCl3) d 4.85 (s, 2H),
7.17 (t, J = 7.3 Hz, 1H), 7.40–7.44 (m, 2H), 7.48–7.52 (m, 2H), 7.57–7.61 (m, 1H),
7.85–7.88 (m, 2H), 7.92 (d, J = 7.6 Hz, 1H); 13C NMR (100 MHz, CDCl3) d 51.15,
119.89, 123.04, 124.56, 124.90, 128.80, 129.58, 132.49, 133.64, 139.90, 140.54,
167.94. Compound 3b: Solid (hexane–chloroform); mp 98 °C; (lit.23 98–
98.5 °C); 1H NMR (400 MHz, CDCl3) d 2.26 (s, 3H), 4.72 (s, 2H), 7.22–7.34 (m,
4H), 7.51 (t, J = 7.6 Hz, 2H), 7.58–7.62 (m, 1H), 7.94 (d, J = 7.3 Hz, 1H); 13C NMR
References and notes
1. Tsuji, J. Palladium Reagents and Catalysis; Wiley: Chichester, 1995.
2. Handbook of Organopalladium Chemistry for Organic Synthesis; Negishi, E., Ed.;
Wiley: New York, 2002.
3. Colquhoun, H. M.; Thompson, D. J.; Twigg, M. V. Carbonylation: Direct Synthesis
of Carbonyl Compounds; Plenum Press: New York, 1991. p 173.
4. For physiological activities of isoindolin-1-ones, see: Takahashi, I.; Kawakami, T.;
Hirano, E.; Yokota, H.; Kitajima, H. Synlett 1996, 353. and references cited therein.
5. Cho, C. S.; Lee, J. W.; Lee, D. Y.; Shim, S. C.; Kim, T. J. Chem. Commun. 1996, 2115.
6. Cho, C. S.; Chu, D. Y.; Lee, D. Y.; Shim, S. C.; Kim, T.-J.; Lim, W. T.; Heo, N. H.
Synth. Commun. 1997, 27, 4141.
(100 MHz, CDCl3)
d 18.34, 53.15, 122.95, 124.33, 126.96, 127.55, 128.30,
128.38, 131.32, 131.80, 132.51, 136.48, 137.09, 141.69, 167.75. Compound 3n:
Solid (hexane–chloroform); mp 88–89 °C; (lit.24 87–89 °C); 1H NMR (400 MHz,
CDCl3) d 4.25 (s, 2H), 4.79 (s, 2H), 7.26–7.38 (m, 6H), 7.43–7.52 (m, 2H), 7.89 (d,
J = 7.1 Hz, 1H); 13C NMR (100 MHz, CDCl3) d 46.48, 49.55, 122.89, 123.96,
127.79, 128.15, 128.26, 128.91, 131.49, 132.69, 137.11, 141.34, 168.62.
23. Yamamoto, I.; Tabo, Y.; Gotoh, H. Tetrahedron Lett. 1971, 2295.
7. Cho, C. S.; Jiang, L. H.; Shim, S. C. Synth. Commun. 1998, 28, 849.
8. Grigg, R.; Zhang, L.; Collard, S.; Keep, A. Tetrahedron Lett. 2003, 44, 6979.
9. Okuro, K.; Inokawa, N.; Miura, M.; Nomura, M. J. Chem. Res. (S) 1994, 372.
10. (a) Cho, C. S.; Lim, D. K.; Zhang, J. Q.; Kim, T.-J.; Shim, S. C. Tetrahedron Lett.
2004, 45, 5653; (b) Cho, C. S.; Patel, D. B.; Shim, S. C. Tetrahedron 2005, 61, 9490.
11. (a) Cho, C. S.; Shim, H. S.; Choi, H.-J.; Kim, T.-J.; Shim, S. C.; Kim, M. C.
Tetrahedron Lett. 2000, 41, 3891; (b) Cho, C. S.; Lim, D. K.; Heo, N. H.; Kim, T.-J.;
24. Wada, Y.; Nagasaki, H.; Tokuda, M.; Orito, K. J. Org. Chem. 2007, 72, 2008.