5102
A.-I. Tsai, C.-P. Chuang / Tetrahedron 64 (2008) 5098–5102
J¼7.6 Hz, 2H, CH2), 3.14 (s, 3H, NCH3), 7.82–7.92 (m, 2H, ArH), 8.01–
8.09 (m, 2H, ArH); 13C NMR (100.6 MHz, CDCl3) d 7.6 (q), 12.8 (q),
20.5 (t), 27.0 (q), 33.4 (t), 71.1 (s), 117.9 (s), 124.4 (2ꢀd), 135.7 (2ꢀd),
143.3 (2ꢀs), 160.8 (s), 170.4 (s), 192.7 (s), 193.3 (2ꢀs). Anal. Calcd for
References and notes
1. (a) Hart, D. J. Science 1984, 223, 883; (b) Neumann, W. P. Synthesis 1987, 665; (c)
Curran, D. P. Synthesis 1988, 417 and 489; (d) Melikyan, G. G. Synthesis 1993,
833; (e) Iqbal, J.; Bhatia, B.; Nayyar, N. K. Chem. Rev. 1994, 94, 519; (f) Snider, B. B.
Chem. Rev. 1996, 96, 339.
C
18H17NO4: C, 69.44; H, 5.50; N, 4.50. Found: C, 69.44; H, 5.50; N, 4.53.
2. (a) The Chemistry of the Quinoid Compounds; Patai, S., Rappoport, Z., Eds.; The
Chemistry of Functional Groups; Wiley: New York, NY, 1988; (b) Thomson, R. H.
Natural Occurring Quinones IV: Recent Advances; Chapman and Hall: London,
1997.
3. (a) Shaw, K. J.; Luly, J. R.; Rapoport, H. J. Org. Chem. 1985, 50, 4515; (b) Murphy,
W. S.; O’Sullivan, P. J. Tetrahedron Lett. 1992, 33, 531; (c) O’Sullivan, P. J.; Moreno,
R.; Murphy, W. S. Tetrahedron Lett. 1992, 33, 535.
4. (a) Yogo, M.; Ito, C.; Furukawa, H. Chem. Pharm. Bull. 1991, 39, 328; (b) Bittner,
S.; Krief, P.; Massil, T. Synthesis 1991, 215; (c) Kno¨lker, H.-J.; O’Sullivan, N.
Tetrahedron 1994, 50, 10893; (d) Åkermark, B.; Oslob, J. D.; Heuschert, U.
Tetrahedron Lett. 1995, 36, 1325; (e) Echavarran, A. M.; Tamayo, N.; De Frutos, O.;
Garcia, A. Tetrahedron 1997, 50, 16835.
5. (a) Oumar-Mahamat, H.; Moustrou, C.; Surzur, J.-M.; Berstrand, M. P. J. Org.
Chem. 1989, 54, 5684; (b) Snider, B. B.; Wan, B. Y. F.; Buckman, B. O.; Foxman, B.
M. J. Org. Chem. 1991, 56, 5328; (c) Citterio, A.; Sebastiano, R.; Carvayal, M. C.
J. Org. Chem. 1991, 56, 5335; (d) Citterio, A.; Sebastiano, R.; Nicolini, M.
Tetrahedron 1993, 49, 7743.
3.3.4. 40-Isobutanoyl-50-isopropyl-10-methyl-spiro[indene-2,30-
pyrrole]-1,20,3(10H)-trione 6d
White crystals; mp 165–166 ꢁC; IR (CHCl3) 2980, 1760, 1715,
1630, 1590 cmꢂ1; 1H NMR (300 MHz, CDCl3) d 1.06 (d, J¼6.8 Hz, 6H,
2ꢀCH3), 1.52 (d, J¼7.3 Hz, 6H, 2ꢀCH3), 2.94 (septet, J¼6.8 Hz, 1H,
CH), 3.26 (s, 3H, NCH3), 3.91 (septet, J¼7.3 Hz,1H, CH), 7.80–7.91 (m,
2H, ArH), 8.01–8.10 (m, 2H, ArH); 13C NMR (75.4 MHz, CDCl3) d 19.1
(2ꢀq), 19.7 (2ꢀq), 27.1 (q), 29.7 (d), 38.0 (d), 71.5 (s), 117.2 (2ꢀd),
124.4 (2ꢀd), 135.5 (s), 143.2 (2ꢀs), 163.1 (s), 170.9 (s), 193.2 (s), 197.8
(2ꢀs). Anal. Calcd for C20H21NO4: C, 70.78; H, 6.24; N, 4.13. Found:
C, 70.74; H, 6.25; N, 4.10.
6. (a) Chuang, C.-P.; Wang, S.-F. Tetrahedron Lett. 1994, 35, 4365; (b) Chuang, C.-P.;
Wang, S.-F. J. Chin. Chem. Soc. 1997, 44, 271; (c) Chuang, C.-P.; Wang, S.-F.
Tetrahedron 1998, 54, 10043; (d) Chuang, C.-P.; Wang, S.-F. Heterocycles 1999,
50, 489; (e) Chuang, C.-P.; Wu, Y.-L.; Jiang, M.-C. Tetrahedron 1999, 55, 11229;
(f) Jiang, M.-C.; Chuang, C.-P. J. Org. Chem. 2000, 65, 5409; (g) Wu, Y.-L.; Chuang,
C.-P.; Lin, P.-Y. Tetrahedron 2001, 57, 5543; (h) Tsai, A.-I.; Wu, Y.-L.; Chuang, C.-P.
Tetrahedron 2001, 57, 7829; (i) Chuang, C.-P.; Wu, Y.-L. Tetrahedron Lett. 2001,
42, 1719; (j) Tseng, C.-C.; Wu, Y.-L.; Chuang, C.-P. Tetrahedron 2002, 58, 7625;
(k) Tseng, C.-M.; Wu, Y.-L.; Chuang, C.-P. Tetrahedron 2004, 60, 12249; (l) Chen,
H.-L.; Lin, C.-Y.; Cheng, Y.-C.; Tsai, A.-I.; Chuang, C.-P. Synthesis 2005, 977;
(m) Lin, C.-Y.; Cheng, Y.-C.; Tsai, A.-I.; Chuang, C.-P. Org. Biomol. Chem. 2006,
1097.
7. (a) Liao, Y.-J.; Wu, Y.-L.; Chuang, C.-P. Tetrahedron 2003, 59, 3511; (b) Chuang,
C.-P.; Wu, Y.-L. Tetrahedron 2004, 60, 1841; (c) Tsai, A.-I.; Lin, C.-H.; Chuang,
C.-P. Heterocycles 2005, 977; (d) Tsai, A.-I.; Chuang, C.-P. Tetrahedron 2006,
62, 2235.
8. (a) Jacobsen, N.; Torsell, K. Acta Chem. Scand. 1973, 27, 3211; (b) Brown, P. M.;
Thomson, R. H. J. Chem. Soc., Perkin Trans. 11976, 997; (c) Citterio, A.; Arnoldi, A.;
Minisci, F. J. Org. Chem. 1979, 44, 2674; (d) Citterio, A.; Vismara, E.; Bernardi, R.
J. Chem. Res., Synop. 1983, 88; (e) Citterio, A.; Vismara, E.; Bernardi, R. J. Chem.
Res., Miniprint 1983, 876; (f) Williams, D. R.; Clark, M. P. Tetrahedron Lett. 1998,
39, 7629.
3.3.5. Ethyl 10-methyl-50-propyl-1,10,20,3-tetrahydro-1,20,3-trioxo-
spiro[indene-2,30-pyrrole]-40-carboxylate 6e
White crystals; mp 146–147 ꢁC; IR (CHCl3) 2975, 1705, 1630,
1430, 1345 cmꢂ1; 1H NMR (400 MHz, CDCl3) d 0.79 (t, J¼7.1 Hz, 3H,
CH3), 1.11 (t, J¼7.5 Hz, 3H, CH3), 1.74 (sextet, J¼7.5 Hz, 2H, CH2), 2.99
(t, J¼7.5 Hz, 2H, CH2), 3.12 (s, 3H, NCH3), 3.91 (q, J¼7.1 Hz, 2H,
OCH2), 7.85–7.91 (m, 2H, ArH), 8.08–8.10 (m, 2H, ArH); 13C NMR
(100.6 MHz, CDCl3) d 13.4 (q), 13.7 (q), 21.5 (t), 27.1 (q), 27.7 (t), 60.1
(t), 70.4 (s),105.9 (s),124.3 (2ꢀd),135.8 (2ꢀd),143.5 (2ꢀs),162.0 (s),
162.9 (s), 170.5 (s), 193.3 (2ꢀs). Anal. Calcd for C19H19NO5: C, 66.85;
H, 5.61; N, 4.10. Found: C, 66.71; H, 5.63; N, 4.08.
3.3.6. Ethyl 10,50-dimethyl-1,10,20,3-tetrahydro-1,20,3-trioxo-
spiro[indene-2,30-pyrrole]-40-carboxylate 6f
White crystals; mp 123–124 ꢁC; IR (KBr) 2980, 1710, 1290, 1170,
1065 cmꢂ1; 1H NMR (400 MHz, CDCl3) d 0.80 (t, J¼7.1 Hz, 3H, CH3),
2.59 (s, 3H, CH3), 3.11 (s, 3H, NCH3), 3.92 (q, J¼7.1 Hz, 2H, OCH2),
7.86–7.88 (m, 2H, ArH), 8.04–8.10 (m, 2H, ArH); 13C NMR (75.4 MHz,
CDCl3) d 12.5 (q), 13.3 (q), 26.8 (q), 60.0 (t), 70.2 (s), 105.8 (s), 124.2
(2ꢀd), 135.8 (2ꢀd), 143.3 (2ꢀs), 158.9 (s), 162.0 (s), 170.0 (s), 193.2
(2ꢀs). Anal. Calcd for C17H15NO5: C, 65.17; H, 4.83; N, 4.47. Found: C,
65.08; H, 4.81; N, 4.43.
9. Manganese(III)-mediated reactions of 1 with b-ketoesters generate indole-4,7-
diones and indole-2,4,7-triones. See: Chuang, C.-P.; Tsai, A.-I. Tetrahedron 2007,
63, 11911.
10. Crystal data for 3a: C15H17NO5, M¼291.30, T¼200(2) K, l¼0.71073 Å, mono-
clinic, space group Pn, a¼7.4869(2) Å, b¼7.8791(2) Å, c¼12.3767(4) Å, a¼90ꢁ,
b¼96.7830(10)ꢁ, g¼90ꢁ, V¼724.99(4) Å3, Z¼2, Dc¼1.334 mg/m3, m¼0.
101 mmꢂ1, F(000)¼308, crystal size 0.75ꢀ0.7ꢀ0.6 mm3, reflections collected
5027, independent reflections 2518 [R (int)¼0.0442], refinement method, full-
matrix least-squares on F2, goodness-of-fit on F2 1.076, final R indices [I>2s(I)]
R1¼0.0552, wR2¼0.1465, R indices (all data) R1¼0.0580, wR2¼0.1507, largest
diff. peak and hole 0.454 and ꢂ0.304 e Åꢂ3. Crystallographic data for the
structure in this paper have been deposited with the Cambridge Crystallo-
graphic Data Centre as supplementary publication no. CCDC 672265. Copies of
the data can be obtained, free of charge, on application to CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK (fax: þ44 (0)1223 336033 or e-mail: deposit@ccdc.
11. Indole-2,4,7-triones 4a and 4b can be produced in much better reaction yields
by the manganese(III)-mediated reaction of 1 with b-ketoesters in CF3CH2OH.
See: Ref. 9.
12. Preliminary communication has been reported. See: Ref. 6i.
13. Similar 1,2-acyl group migration has been reported. See: Chuang, C.-P.; Tsai,
A.-I. Tetrahedron 2007, 63, 9712.
3.3.7. Ethyl 10-ethyl-50-phenyl-1,10,20,3-tetrahydro-1,20,3-trioxo-
spiro[indene-2,30-pyrrole]-40-carboxylate 6g
White crystals; mp 185–186 ꢁC; IR (KBr) 2990, 1715, 1380, 1270,
1075 cmꢂ1; 1H NMR (400 MHz, CDCl3) d 0.65 (t, J¼7.1 Hz, 3H, CH3),
1.02 (t, J¼7.1 Hz, 3H, CH3), 3.42 (q, J¼7.1 Hz, 2H, NCH2), 3.76 (q,
J¼7.1 Hz, 2H, OCH2), 7.53 (br s, 5H, ArH), 7.87–7.93 (m, 2H, ArH),
8.08–8.14 (m, 2H, ArH); 13C NMR (75.4 MHz, CDCl3) d 12.9 (q), 13.8
(q), 36.4 (t), 59.9 (t), 70.7 (s), 107.6 (s), 124.1 (2ꢀd), 128.2 (2ꢀd),
128.4 (s), 128.7 (2ꢀd), 130.0 (d), 135.7 (2ꢀd), 143.3 (2ꢀs), 159.3 (s),
161.1 (s), 170.0 (s), 192.7 (2ꢀs). Anal. Calcd for C23H19NO5: C, 70.94;
H, 4.92; N, 3.60. Found: C, 70.81; H, 4.97; N, 3.53.
14. (a) Zhang, Y.; Flowers, R. A., II. J. Org. Chem. 2003, 68, 4560; (b) Zhang, Y.; Raines,
A. J.; Flowers, R. A., II. Org. Lett. 2003, 5, 2363. Also see: Ref. 7d.
15. Kallmeyer, H.-J.; Tappe, C. Arch. Pharm. 1986, 319, 421.
16. Kobayashi, K.; Suzuki, M.; Takeuchi, H.; Konishi, A.; Sakurai, H.; Suginome, H.
J. Chem. Soc., Perkin Trans. 1 1994, 1099.
Acknowledgements
17. (a) Tanemura, K.; Suzuki, T.; Nishida, Y.; Satsumabayashi, K.; Horaguchi, T. Chem.
Commun. 2004, 470; (b) Meshram, H. M.; Reddy, P. N.; Sadashiv, K.; Yadav, J. S.
Tetrahedron Lett. 2005, 46, 623.
We are grateful to the National Science Council of the ROC for
financial support (Grant No. NSC-95-2113-M-006-010).