2528
A. Zea et al. / Tetrahedron 67 (2011) 2513e2529
4.5.10. (þ)-1-Benzyl-3-(4,5-dihydroxy-10-oxo-9,10-dihydro-an-
thracen-9-yl)-pyrrolidine-2,5-dione (15b)28. Obtained in 92% yield
5.07e5.08 (d, J¼3.0 Hz, 1H, major diastereomer), 5.28e5.37 (m, 1H,
both diastereomers), 6.48e6.50 (d, J¼7.5 Hz, 1H, minor di-
astereomer), 6.77e6.80 (d, J¼7.5 Hz, 1H, major diastereomer),
6.84e7.36 (m, 12H, both diastereomers), 7.50e7.55 (t, J¼7.5 Hz, 1H,
and 85% ee from 13b and 1b. Yellow solid. [
a
]
20 þ38.5 (c 1.0, CHCl3).
D
1H NMR (300 MHz)
d
1.98e2.05 (dd, J¼15.0, 6.0 Hz, 1H), 2.30e2.38
(dd, J¼15.0, 9.0 Hz, 1H), 3.31 (m, 1H), 4.56 (s, 1H), 4.58 (s, 1H), 5.08
(d, J¼3.0 Hz, 1H), 6.59e6.56 (d, J¼9.0 Hz, 1H), 6.84e6.81
(d, J¼9.0 Hz, 1H), 6.93e6.96 (d, J¼9.0 Hz, 1H), 7.00e7.03
(d, J¼9.0 Hz, 1H), 7.26e7.33 (m, 6H), 7.51e7.57 (t, J¼9.0 Hz, 1H). 13C
both diastereomers). 13C NMR (100.6 MHz)
d 29.8, 42.6, 51.3, 116.0,
116.7, 117.4, 118.4, 118.9, 119.1, 123.1, 128.0, 130.6, 132.7, 136.9, 137.6,
139.8, 143.8, 163.3, 163.6, 173.8, 176.3, 193.4. HRMS (ESI) calcd from
C26H20NO5 (MꢀH)ꢀ: 426.1347; found: 426.1346.
NMR (100.6 MHz)
d 29.4, 42.0, 42.8, 51.1, 115.8, 116.4, 117.1, 117.8,
118.9, 119.1, 128.3, 128.8, 129.2, 135.5, 137.0, 137.4, 139.6, 144.3, 163.1,
163.3, 174.9, 177.3, 193.3. HRMS (ESI) calcd from C25H20NO5
(MþH)þ: 414.1336; found: 414.1337. Daicel ChiralpakÒ IB column,
i-PrOH/hexane 10:90, flow rate 1 mL/min, UV detection at 254 nm,
tmajor¼30.2 min, tminor¼36.8 min.
Acknowledgements
We thank the Spanish Ministry of Science and Innovation
(MICINN) for financial support (Project AYA2009-13920-C02-02).
We are also grateful to G. Valero for his preliminary work with
ꢀ
4.5.11. (þ)-1-(3-Chlorophenyl)-3-(4,5-dihydroxy-10-oxo-9,10-dihy-
anthrones, and to the ‘Serveis Científico-Tecnics de la Universitat de
dro-anthracen-9-yl)-pyrrolidine-2,5-dione (15c). Obtained in 92%
Barcelona’ for their invaluable technical assistance.
20
yield and 22% ee from 13c and 1b. Yellow solid. [
CHCl3). 1H NMR (300 MHz)
2.53e2.58 (dd, J¼9.0, 6.0 Hz, 1H), 3.52 (m, 1H), 5.18 (d, J¼3.0 Hz,
1H), 7.59e6.91 (m, 10H). 13C NMR (100.6 MHz)
32.4, 45.2, 53.9,
a
]
þ11.6 (c 1.0,
D
d
2.47e2.52 (dd, J¼9.0, 6.0 Hz, 1H),
References and notes
d
1. Rodd’s Chemistry of Organic Compounds; Coffey, S., Ed.; Elsevier: New York, NY,
1979; Vol. III, Part H.
118.6, 119.3, 120.0, 121.1, 121.6, 121.8, 127.4, 129.5, 132.0, 133.1, 135.3,
137.7, 139.6, 140.2, 142.4, 146.5, 165.9, 166.2, 176.4, 178.9, 196.0.
HRMS (ESI) calcd from C24H15ClNO5 (MꢀH)ꢀ: 432.0644; found:
432.0638. HPLC conditions: Daicel ChiralpakÒ IB column, i-PrOH/
2. For two recent references, see: (a) Srinivas, K.; Yesudas, K.; Bhanuprakash, K.;
Rao, J. V.; Giribabu, L. J. Phys. Chem. C 2009, 113, 20117e20126; (b) Iwaura, R.;
Ohnishi-Kameyama, M.; Lizawa, T. Chem.dEur. J. 2009, 15, 3729e3735.
3. See, for instance: (a) Krenn, L.; Pradhan, R.; Presser, A.; Reznicek, G.; Kopp, B.
Chem. Pharm. Bull. 2004, 52, 391e393; (b) Diaz, F.; Chai, H.-B.; Mi, Q.; Su, B.-N.;
Vigo, J. S.; Graham, J. G.; Cabieses, F.; Farnsworth, N. R.; Cordell, G. A.; Pezzuto,
J. M.; Swanson, S. M.; Kinghorn, A. D. J. Nat. Prod. 2004, 67, 352e356.
hexane 10:90, flow rate 1 mL/min, UV detection at 254 nm, tmajor
33.3 min, tminor¼40.8 min.
¼
€
4. (a) Muller, K.; Prinz, H. J. Med. Chem. 1997, 40, 2780e2787; (b) Cameron, D. W.;
4.5.12. (þ)-3-(4,5-Dihydroxy-10-oxo-9,10-dihydro-anthracen-9-yl)-
Skene, C. E. Aust. J. Chem. 1996, 49, 617e624; (c) Huang, H.-S.; Hwang, J.-M.; Jen,
Y.-M.; Lin, J.-J.; Lee, K.-Y.; Shi, C.-H.; Hsu, H.-C. Chem. Pharm. Bull. 2001, 49,
969e973.
5. (a) Hoffman, E. J. Cancer and the Search for Selective Biochemical Inhibitors, 2nd
ed.; CRC: Boca Raton, 2007; (b) Kren, V.; Rezanka, T. FEMS Microbiol. Rev. 2008,
32, 858e889; (c) Bringman, S.; Maksimenka, K.; Knauer, M.; Abegaz, B. M. Nat.
1-(4-methoxyphenyl)-pyrrolidine-2,5-dione (15d)28. Obtained in
20
94% yield and 97% ee from 13d and 1b. Yellow solid. [
a
]
þ74.9
D
(c 1.0, CHCl3). 1H NMR (300 MHz)
d
2.16e2.23 (dd, J¼15.0, 6.0 Hz,
1H), 2.47e2.54 (dd, J¼15.0, 6.0 Hz, 1H), 3.49 (m, 1H), 3.83 (s, 3H),
5.19 (d, J¼3.0 Hz, 1H), 6.94e7.02 (m, 5H), 7.09 (d, J¼6.0 Hz, 1H),
7.46e7.48 (d, J¼6.0 Hz, 1H), 7.49e7.51 (d, J¼6.0 Hz, 1H), 7.57e7.61
€
Prod. Rep. 1999, 25, 696e716; (d) Muller, K. Appl. Microbiol. Biotechnol. 2001, 56,
9e16; (e) Pecere, T.; Gazzola, M. V.; Mucignat, C.; Parolin, C.; Dalla Vecchia, F.;
Cavaggini, A.; Basso, G.; Diaspro, A.; Salvato, B.; Carli, M.; Pulci, G. Cancer Res.
2000, 60, 2800e2804; (f) Shiono, Y.; Shino, N.; Seo, S.; Oka, S.; Yamazaki, Y.
Z.Naturforsch. 2002, 57c, 923e929; (g) Zuse, A.; Schmidt, D.; Baasner, S.; Bohm,
K. J.; Muller, K.; Gerlach, M.; Gunther, E. G.; Unger, E.; Prinz, H. J. Med. Chem.
2007, 50, 6059e6066; (h) Prinz, H.; Ishii, Y.; Hirano, T.; Stoiber, T.; Camacho
Gomez, J. A.; Schmidt, P.; Dussmann, H.; Burger, A. M.; Prehn, J. H. M.; Gunther,
E. G.; Unger, E.; Umezawa, K. J. Med. Chem. 2003, 46, 3382e3394.
6. (a) Valero, G.; Balaguer, A.-N.; Moyano, A.; Rios, R. Tetrahedron Lett. 2008, 49,
6559e6562; (b) Valero, G.; Schimer, J.; Cisarova, I.; Vesely, J.; Moyano, A.; Rios,
R. Tetrahedron Lett. 2009, 50, 1943e1946; (c) Balaguer, A.-N.; Companyo, X.;
Calvet, T.; Font-Bardía, M.; Moyano, A.; Rios, R. Eur. J. Org. Chem. 2009, 199e203;
(d) Companyo, X.; Valero, G.; Crovetto, L.; Moyano, A.; Rios, R. Chem.dEur. J.
2009, 15, 6564e6568; (e) Companyo, X.; Hejnova, M.; Kamlar, M.; Vesely, J.;
Moyano, A.; Rios, R. Tetrahedron Lett. 2009, 50, 5021e5024; (f) Companyo, X.;
Balaguer, A.-N.; Cardenas, F.; Moyano, A.; Rios, R. Eur. J. Org. Chem. 2009,
3075e3080; (g) Alba, A.-N.; Companyo, X.; Moyano, A.; Rios, R. Chem.dEur. J.
2009, 15, 7035e7038; (h) Alba, A.-N.; Companyo, X.; Moyano, A.; Rios, R.
Chem.dEur. J. 2009, 15, 11095e11099; (i) El-Hamdouni, N.; Companyo, X.; Rios,
R.; Moyano, A. Chem.dEur. J. 2010, 16, 1142e1148; (j) Alba, A.-N. R.; Companyo,
(t, J¼6.0 Hz, 2H). 13C NMR (100.6 MHz)
d 29.7, 42.5, 51.2, 55.7, 114.8,
€
116.7, 117.3, 118.2, 118.9, 119.3, 124.2, 127.7, 136.9, 137.5, 139.9, 144.1,
159.9, 163.2, 163.5, 174.5, 176.9, 193.4. HRMS (ESI) calcd from
C25H20NO6 (MþH)þ: 430.1285; found: 430.1288. HPLC conditions:
Daicel ChiralpakÒ IB column, i-PrOH/hexane 10:90, flow rate 1 mL/
min, UV detection at 254 nm, tmajor¼31.7 min, tminor¼38.8 min.
€
€
ꢁ
€
€
ꢁ
4.5.13. (þ)-1-(4-Bromophenyl)-3-(4,5-dihydroxy-10-oxo-9,10-dihy-
dro-anthracen-9-yl)-pyrrolidine-2,5-dione (15f)28. Obtained in 91%
ꢁ
ꢁ
ꢁ
20
yield and 96% ee from 13f and 1b. Yellow solid. [
a
]
D
þ35.8 (c 0.9,
ꢁ
CHCl3). 1H NMR (300 MHz)
d
2.17e2.25 (dd, J¼18.0, 6.0 Hz, 1H),
ꢁ
ꢁ
2.48e2.57 (dd, J¼18.0, 9.0 Hz, 1H), 3.47e3.52 (m, 1H), 5.17
(d, J¼3.0 Hz, 1H), 6.89e6.92 (d, J¼9.0 Hz, 1H), 6.98e7.02 (m, 4H),
7.06e7.08 (d, J¼6.0 Hz, 1H), 7.44e7.48 (t, J¼6.0 Hz, 1H), 7.56e7.61
ꢁ
ꢁ
ꢁ
(m, 3H). 13C NMR (100.6 MHz)
d
29.8, 42.6, 51.3, 116.0, 116.7, 117.4,
X.; Valero, G.; Moyano, A.; Rios, R. Chem.dEur. J. 2010, 16, 5354e5361; (k) Alba,
A.-N. R.; Valero, G.; Calvet, T.; Font-Bardía, M.; Moyano, A.; Rios, R. Chem.dEur.
J. 2010, 16, 9884e9889 For an account, see: (l) Valero, G.; Alba, A.-N. R.;
118.4, 118.9, 119.1, 123.1, 128.0, 130.6, 132.7, 136.9, 137.6, 139.8, 143.8,
163.3, 163.6, 173.8, 176.3, 193.4. HRMS (ESI) calcd from C24H15BrNO5
(MꢀH)ꢀ: 476.0139; found: 476.0129. HPLC conditions: Daicel
ChiralpakÒ IB column, i-PrOH/hexane 10:90, flow rate 1 mL/min,
UV detection at 254 nm, tmajor¼37.3 min, tminor¼56.3 min.
ꢁ
Companyo, X.; Bravo, N.; Moyano, A.; Rios, R. Synlett 2010, 1883e1908.
7. cf. (a) Meek, J. S.; Evans, W. B.; Godefroi, V.; Benson, W. R.; Wilcox, M. F.; Clark,
W. G.; Tiedeman, T. J. Org. Chem. 1961, 26, 4281e4285; (b) Cohen, D.; Millar, I. T.;
Richards, K. E. J. Chem. Soc. C 1968, 793e795.
8. Baik, W.; Yoon, C. H.; Koo, S.; Kin, H.; Kim, J.; Kim, J.; Hong, S. Bull. Korean Chem.
Soc. 2004, 25, 491e500.
9. Preliminary communication: Alba, A.-N.; Bravo, N.; Moyano, A.; Rios, R. Tetra-
hedron Lett. 2009, 50, 3067e3069.
4.5.14. 3-(4,5-Dihydroxy-10-oxo-9,10-dihydro-anthracen-9-yl)-1-
((R)-1-phenylethyl)-pyrrolidine-2,5-dione (15h). Obtained in 77%
yield as a 1.25:1 mixture of the (R,S)- and (R,R)-diastereomers from
10. N,N0-Bis(3,5-bis(trifluoromethyl)phenyl) thiourea Kotke, A.; Schreiner, P. R.
Tetrahedron 2005, 61, 434e439.
(R)-13h and 1b. 1H NMR (300 MHz)
d
1.70e1.73 (d, J¼7.2 Hz, 3H,
11. Shen, J.; Nguyen, T. T.; Goh, Y.-P.; Ye, W.; Fu, X.; Xu, J.; Tan, C.-H. J. Am. Chem. Soc.
2006, 128, 13692e13693.
minor diastereomer), 1.72e1.74 (d, J¼7.2 Hz, 3H, major di-
astereomer), 1.91e1.94 (dd, J¼5.1, 2.4 Hz, 1H, minor diastereomer),
1.97e2.00 (dd, J¼5.4, 2.4 Hz, 1H, major diastereomer), 2.24e2.29
(dd, J¼9.6, 3.9 Hz, 1H, major diastereomer), 2.30e2.35 (dd, J¼9.3,
3.9 Hz, 1H, minor diastereomer), 3.22e3.29 (m, 1H, both dia-
stereomers), 5.03e5.04 (d, J¼3.0 Hz, 1H, minor diastereomer),
12. Wu, C.; Li, W.; Yang, J.; Liang, X.; Ye, J. Org. Biomol. Chem. 2010, 8, 3244e3250.
13. For reviews on organocatalysis dealing with enantioselective iminium catalysis,
€
see: (a) Erkkila, A.; Majander, I.; Pihko, P. M. Chem. Rev. 2007, 107, 5416e5470;
(b) Tsogoeva, S. B. Eur. J. Org. Chem. 2007, 1701e1716; (c) Melchiorre, P.; Marigo,
M.; Carlone, A.; Bartoli, G. Angew. Chem., Int. Ed. 2008, 47, 6138e6171;
(d) Bartoli, G.; Melchiorre, P. Synlett 2008, 1759e1772; (e) Bertelsen, S.;
Jérgensen, K. A. Chem. Soc. Rev. 2009, 38, 2178e2189; (f) Enders, D.; Wang, C.;