2736
X. Huang, R. Shen
PAPER
Eds.; Pergamon: New York, 1984, Chap. 2.23, 647–736.
7,7-Dimethyl-4-[(naphthalen-1-yl)methyl]-7,8-dihydro-2H-
chromene-2,5(6H)-dione (5i)
Mp 136–137 °C.
IR (KBr): 2958, 1746, 1674, 1542, 1410 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.70–7.88 (m, 3 H), 7.41–7.49 (m,
3 H), 7.25–7.27 (m, 1 H), 5.45 (s, 1 H), 4.72 (s, 2 H), 2.76 (s, 2 H),
2.50 (s, 2 H), 1.66 (s, 6 H).
13C NMR (100 MHz, CDCl3): d = 195.8, 173.3, 159.9, 158.0, 133.9,
132.8, 131.8, 128.8, 128.0, 127.9, 126.3, 125.8, 125.5, 123.7, 113.2,
112.8, 52.6, 42.7, 37.2, 31.7, 28.1.
(c) Hepworth, J. D. In Comprehensive Heterocyclic
Chemistry, Vol. 3, Part 2B; Katritzky, A. R.; Rees, C. W.,
Eds.; Pergamon: New York, 1984, Chap. 2.24, 737–884.
(d) Stauton, J. In Comprehensive Organic Chemistry, Vol. 4;
Sammes, P. G., Ed.; Pergamon: Oxford, 1979, 629–646.
(2) (a) Posner, G. H.; Haces, A.; Harrison, W.; Kinter, C. M. J.
Org. Chem. 1987, 52, 4836. (b) Markó, I. E.; Seres, P.;
Evans, G. R.; Swarbrick, T. M. Tetrahedron Lett. 1993, 34,
7305. (c) Markó, I. E.; Evans, G. R. Tetrahedron Lett. 1993,
34, 7309. (d) Kiang, A. K.; Tan, S. F.; Wong, W. S. J. Chem.
Soc. 1971, 2721. (e) Tam, T. F.; Coles, P. Synthesis 1988,
383.
MS: m/z (%) = 332 (M+, 90), 304 (100).
HRMS (EI): m/z calcd for C22H20O3: 332.1412; found: 332.1409.
(3) (a) Chen, C. H.; Liao, C. C. Org. Lett. 2000, 2, 2049.
(b) Hsung, R. P.; Shen, H. C.; Douglas, C. J.; Morgan, C. D.;
Degen, S. J.; Yao, L. J. J. Org. Chem. 1999, 64, 609.
(c) Danieli, B.; Lesma, G.; Martinelli, M.; Pasarella, D.;
Peretto, I.; Silvani, A. Tetrahedron 1998, 54, 14081.
(4) (a) Hill, R. A. Prog. Chem. Nat. Prod. 1986, 49, 1.
(b) Schultz, A. Z. Chem. Rev. 1973, 73, 385.
7,7-Dimethyl-4-octyl-7,8-dihydro-2H-chromene-2,5(6H)-dione
(5j)
Oil.
IR (neat): 2962, 1750, 1679, 1616, 1540 cm–1.
1H NMR: d = 6.00 (s, 1 H), 2.86 (t, J = 8.0 Hz, 2 H), 2.73 (s, 2 H),
2.42 (s, 2 H), 1.44–1.51 (m, 2 H), 1.26–1.40 (m, 10 H), 1.13 (s, 6
H), 0.88 (t, J = 7.2 Hz, 3 H).
13C NMR: d = 195.2, 173.5, 160.2, 160.1, 113.3, 111.8, 52.7, 42.8,
34.4, 31.8, 31.6, 29.4, 29.3, 29.2, 29.00, 28.0, 22.6, 14.1.
(c) Kozikowski, A. P.; Campiani, G.; Sun, L.-Q.; Wang, S.;
Saxena, A.; Doctor, B. P. J. Am. Chem. Soc. 1996, 118,
11357. (d) Dickinson, J. M. Nat. Prod. Rep. 1993, 10, 71.
(e) Bennasar, M. L.; Zulaica, E.; Juan, C.; Alonso, Y.;
Bosch, J. J. Org. Chem. 2002, 67, 7465. (f) Semple, G.;
Andersson, B.-M.; Chhajlani, V.; Georgsson, J.;
Johannsson, M. J.; Rosenquist, A.; Swanson, L. Bioorg.
Med. Chem. Lett. 2003, 13, 1141. (g) Palow, J. J.;
Kurumbail, R. G.; Stegeman, R. A.; Stevens, A. M.;
Stallings, W. C.; South, M. S. J. Med. Chem. 2003, 46,
4696. (h) Fossa, P.; Menozzi, G.; Dorigo, P.; Floreani, M.;
Mosti, L. Bioorg. Med. Chem. 2003, 11, 4749.
MS: m/z (%) = 304 (M+, 24), 276 (34), 191 (100).
Ethyl (2E,4Z)-4-Acetyl-2-benzyl-5-hydroxy-3-methylhexa-2,4-
dienoate and Ethyl (2Z,4Z)-4-Acetyl-2-benzyl-5-hydroxy-3-
methylhexa-2,4-dienoate [(E/Z)-9]
A solution of ethyl 2-benzylbuta-2,3-dienoate (1a; 121 mg, 0.6
mmol), pentane-2,4-dione (51 mg, 0.5 mmol) and K2CO3 (7 mg, 0.1
equiv) in acetone (0.8 mL) was heated to 40 °C with stirring. After
the reaction was complete (48 h, monitored by TLC, eluent: 6:1 PE–
EtOAc), the solvent was evaporated and the crude product was pu-
rified by chromatography on silica gel (6:1 PE–EtOAc) to afford 9;
yield: 128 mg (85%); oil.
(5) (a) Vara Prasad, J. V. N.; Para, K. S.; Lunney, E. A.;
Ortwine, D. F.; Dunbar, J. B. J. r.; Ferguson, D.; Tummino,
P. J.; Hupe, D.; Tait, B. D.; Domagala, J. M.; Humblet, C.;
Bhat, T. N.; Liu, B.; Guerin, D. M. A.; Baldwin, E. T.;
Erickson, J. W.; Sawyer, T. K. J. Am. Chem. Soc. 1994, 116,
6989. (b) Thaisrivongs, S.; Janakiraman, M. N.; Chong, K.-
T.; Tomich, P. K.; Dolak, L. A.; Turner, S. R.; Strohbach, J.
W.; Lynn, J. C.; Horng, M.-M.; Hinshaw, R. R.;
IR (neat): 3355, 2981, 2921, 1714, 1603, 1495, 1416, 1266 cm–1.
1H NMR: d = 16.46 (s, 0.5 H), 16.16 (s, 0.5 H), 7.20–7.29 (m, 4 H),
7.05–7.08 (m, 1 H), 4.18 (q, J = 7.6 Hz, 1 H), 4.02 (q, J = 7.6 Hz,
1 H), 3.80 (s, 1 H), 3.57 (s, 1 H), 2.12 (s, 1.5 H), 2.02 (s, 3 H), 2.01
(s, 1.5 H), 1.91 (s, 3 H), 1.20 (t, J = 6.8 Hz, 1.5 H), 1.09 (t, J = 6.8
Hz, 1.5 H).
13C NMR: d = 189.4, 188.9, 168.8, 168.7, 140.1, 138.7, 138.6,
137.7, 134.6, 133.7, 128.5, 128.4, 128.2, 126.3, 126.2, 115.2, 114.3,
60.6, 60.5, 36.9, 35.7, 23.1, 22.9, 22.8, 21.4, 14.0, 13.9.
Watenpaugh, K. D. J. Med. Chem. 1996, 39, 2400.
(c) Hagen, S. E.; Vara Prasad, J. V. N.; Boyer, F. E.;
Domagala, J. M.; Ellsworth, E. L.; Gajda, C.; Hamilton, H.
W.; Markoski, L. J.; Steinbaugh, B. A.; Tait, B. D.; Lunney,
E. A.; Tummino, P. J.; Ferguson, D.; Hupe, D.; Nouhan, C.;
Gracheck, S. J.; Saunders, J. M.; VanderRoest, S. J. Med.
Chem. 1997, 40, 3707.
(6) Schlingmann, G.; Milne, L.; Carter, G. T. Tetrahedron 1998,
54, 13013.
MS: m/z (%) = 302 (M+, 6), 211 (91), 43 (100).
(7) (a) Cutler, H. G.; Cox, R. H.; Crumley, F. G.; Cole, P. O.
Agric. Biol. Chem. 1986, 50, 2943. (b) Claydon, N.; Allan,
M. Trans. Br. Mycol. Soc. 1987, 88, 503. (c) Simon, A.;
Dunlop, R. W.; Ghisalberti, E. L.; Silvasithamparam, K. Soil
Biol. Biochem. 1988, 20, 263. (d) Evidente, A.; Cabras, A.;
Maddau, L.; Serra, S.; Andolfi, A.; Motta, A. J. Agric. Food
Chem. 2003, 51, 6957.
HRMS (EI): m/z calcd for C18H22O4: 302.1518; found: 302.1519.
Acknowledgment
We are grateful to the National Natural Science Foundation of
China (Project No. 20472072, 20332060) for financial support.
(8) (a) Abraham, W. R.; Arfmann, H. Phytochemistry 1988, 27,
3310. (b) Barrero, A. F.; Oltra, J. E.; Herrador, M. M.;
Sanchez, J. F.; Quilez, J. F.; Rojas, F. J.; Reyes, J. F.
Tetrahedron 1993, 49, 141. (c) Yao, T.; Larock, R. C. J.
Org. Chem. 2003, 68, 5936. (d) Fairlamb, I. J. S.; Marrison,
L. R.; Dickinson, J. M.; Lu, F.-J.; Schmidt, J. P. Bioorg.
Med. Chem. 2004, 12, 4285.
(9) Shi, X.; Leal, W. S.; Liu, Z.; Schrader, E.; Meinwald, J.
Tetrahedron Lett. 1995, 36, 71.
(10) Marrison, L. R.; Dickinson, J. M.; Fairlamb, I. J. Bioorg.
References
(1) For comprehensive reviews on 2-pyrones, see: (a) Brogden,
P. J.; Gabbutt, C. D.; Hepworth, J. D. In Comprehensive
Heterocyclic Chemistry, Vol. 3, Part 2B; Katritzky, A. R.;
Rees, C. W., Eds.; Pergamon: New York, 1984, Chap. 2.22,
573–646. (b) Ellis, G. P. In Comprehensive Heterocyclic
Chemistry, Vol. 3, Part 2B; Katritzky, A. R.; Rees, C. W.,
Med. Chem. Lett. 2003, 13, 2667.
Synthesis 2006, No. 16, 2731–2737 © Thieme Stuttgart · New York