S. Kotha et al. / Tetrahedron 67 (2011) 4616e4619
4619
combined organic layer was washed with water followed by brine.
The solvent was evaporated under reduced pressure and the
resulting residue was purified by a silica gel column chromatog-
raphy (20% ethyl acetate/petroleum ether) to deliver 11 (188 mg,
65%) as a white crystalline solid (space group Pꢂ1, crystallization
solvent: ethyl acetate/petroleum ether). The details of this X-ray
crystallographic data of compound 11 have also been deposited
with the Cambridge Crystallographic Data Center as Supplemen-
tary Publication No. CCDC-780702. Mp: 155e158 ꢀC, 1H NMR
CDCl3)
13C NMR (100.6 MHz, CDCl3)
(KBr): nmax 1761, 1445, 1266 cmꢂ1
d
1.5 (d, J¼6.4 Hz, 6H), 2.3e2.5 (m, 4H), 4.6e4.7 (m, 2H) ppm,
d
21.0, 40.8, 53.4, 75.6, 174.4 ppm, IR
.
Acknowledgements
We would like to thank the DST (New Delhi) for financial sup-
port. M.K.D. thank CSIR (New Delhi) for the award of research fel-
lowship. S.K. thanks DST for the award of J.C. Bose Fellowship. We
would like to thank Prof. Dr. R. Butcher for his help in solving the
crystal data of compound 14a.
(400 MHz, CDCl3)
d
1.20 (d, J¼5.8 Hz, 3H), 1.38 (dd, J1¼17.2 Hz,
J2¼11.3 Hz, 2H), 1.41 (d, J¼6.2, 3H), 2.05e2.14 (m, 4H), 2.29 (dd,
J1¼11.2 Hz, J2¼5.5 Hz, 1H), 2.56 (s, 1H), 2.73 (d, J¼11.7 Hz, 1H), 3.31
(br s, 1H), 3.40e3.41 (m, 1H), 3.8e3.9 (m, 1H), 4.46e4.53 (m, 1H),
4.80e4.83 (m, 1H) ppm, 13C NMR (100.6 MHz, CDCl3)
d 20.8, 25.0,
References and notes
34.0, 34.5, 37.3, 38.2, 44.5, 51.9, 54.1, 55.3, 65.4, 73.9, 79.7, 176.0,
180.7 ppm, IR (KBr): nmax 1760, 1442, 1256 cmꢂ1, HRMS (QTOF ESþ):
m/z calcd for C15H21O5: 281.1389; found: 281.1402 [MþH]þ.
1. (a) Zheng, M.; Zhang, X.; Zhao, M.; Chang, H. W.; Wang, W.; Wang, Y.; Peng,
S. Bioorg. Med. Chem. 2008, 16, 9574; (b) Durr, H.; Gleiter, R. Angew. Chem.,
Int. Ed. Engl. 1978, 17, 559.
2. (a) Cox, R. J. Non-Silver Photography Processes; Academic: London, 1975; (b)
Brown, G. H. Photochromism; Wiley: New York, NY, 1971.
3.1.3. Bis-lactonization of diethyl 2,2-diallylmalonate (14aec). A
mixture of diethyl 2,2-diallylmalonate 1317 (500 mg, 2.08 mmol)
and concd H2SO4 (11 mL) was stirred at 70 ꢀC. At the conclusion of
the reaction (TLC monitoring, 2.5 h), the reaction mixture was
quenched with aq saturated NaHCO3 solution. The reaction mixture
was extracted with ethyl acetate (3ꢁ25 mL), combined organic
layer was washed with water followed by brine. The solvent was
evaporated under reduced pressure and the resulting residue was
purified by a silica gel column chromatography (15e25% ethyl ac-
etate/petroleum ether) to give 14a (150 mg), 14b (73 mg), and 14c
(75 mg) in 2:1:1 ratio as a white crystalline solid. The overall yield is
78%. The X-ray crystallographic details of compound 14a have also
been deposited with the Cambridge Crystallographic Data Center as
Supplementary Publication No. CCDC-780703 (space group P41212,
crystallization solvent: ethyl acetate/petroleum ether), compound
3. (a) Midland, S. L.; Keen, N. T.; Sims, J. J. J. Org. Chem. 1995, 60, 1118; (b) Midland,
S. L.; Keen, N. T.; Sims, J. J.; Midland, M. M.; Stayton, M. M.; Burton, V.; Smith,
M. J.; Mazzola, E. P.; Graham, K. J.; Clardy, J. J. Org. Chem. 1993, 58, 2940.
4. De La Torre, M. C.; Pascual, C.; Rodriguez, B.; Piozzi, F.; Savona, G.; Perales, A.
Phytochemistry 1986, 25, 1397.
5. (a) Wood, J. L.; Jeong, S.; Salcedo, A.; Jenkins, J. J. Org. Chem. 1995, 60, 286; (b)
Honda, T.; Mizutani, H.; Kanai, K. J. Org. Chem. 1996, 61, 9374.
6. Cimanga, K.; Hermans, N.; Apers, S.; Van Miert, S.; Van den Heuvel, H.; Claeys,
M.; Pieters, L.; Vlietinck, A. J. Nat. Prod. 2003, 66, 97.
7. Su, J. Y.; Zhong, Y. L.; Zeng, L. M. J. Nat. Prod. 1993, 56, 288.
8. Caloprisco, E.; Fourneron, J.-D.; Faure, R.; Demarne, F. E. J. Agric. Food Chem.
2002, 50, 78.
9. (a) Fristad, W. E.; Peterson, J. R. J. Org. Chem. 1985, 50, 10; (b) Heiba, E. I.; Dessau,
R. M.; Koehl, W. J., Jr. J. Am. Chem. Soc. 1968, 90, 5905; (c) Bush, J. B., Jr.; Fink-
beiner, H. J. Am. Chem. Soc. 1986, 108, 5903.
10. Citterio, A.; Sebastiano, R.; Nicolini, M.; Santi, R. Synlett 1990, 42.
11. Alonso, F.; Melendez, J.; Yus, M. Synlett 2008, 1627.
12. (a) Kotha, S.; Halder, S. Synlett 2010, 337; (b) Kotha, S.; Meshram, M.; Tiwari, A.
Chem. Soc. Rev. 2009, 38, 2065; (c) Kotha, S.; Mandal, K. Chem.dAsian J. 2009, 4,
354; (d) Kotha, S.; Lahiri, K. Synlett 2007, 2767; (e) Kotha, S.; Lahiri, K. Eur. J. Org.
Chem. 2007, 1221; (f) Kotha, S.; Deb, A. C.; Lahiri, K.; Manivannan, E. Synthesis
2009, 165.
13. Fringuelli, F.; Taticchi, A. The DielseAlder Reaction: Selected Practical Methods;
John Wiley, Ltd: New York, NY, 2002.
14. (a) Janus, E.; Goc-Maciejewska, I.; Lozynski, M.; Permak, J. Tetrahedron Lett.
2006, 47, 4079; (b) Lowe, A. J.; Dyson, G. A.; Pfeffer, F. M. Org. Biomol. Chem.
2007, 5, 1343.
15. (a) Eliel, E. L.; Wilen, S. H.; Mander, L. N. Stereochemistry of Organic Compounds;
John Wiley: New York, NY, 2003; p 901; (b) Love, B. Chem. Ind. 1964, 193.
16. Hirao, K.; Ohuchi, Y.; Yonemitsu, O. J. Chem. Soc., Chem. Commun. 1982, 99.
17. Pihko, P. M. Hydrogen Bonding in Organic Synthesis; Wiley-VCH GmbH & KGaA:
Weinheim, 2009; p 7.
14a: mp: 118e119 ꢀC, 1H NMR (400 MHz, CDCl3)
d
1.4 (d, J¼6.1 Hz,
3H), 1.5 (d, J¼6.4 Hz, 3H), 1.92 (dd, J1¼12.9 Hz, J2¼9.8 Hz, 1H), 2.34
(dd, J1¼13.4 Hz, J2¼6.7 Hz, 1H) 2.60 (dd, J1¼13.1 Hz, J2¼8.0 Hz, 1H),
2.82 (dd, J1¼12.8 Hz, J2¼5.8 Hz, 1H), 4.6e4.7 (m, 1H), 4.9e5.0 (m,
1H) ppm, 13C NMR (100.6 MHz, CDCl3)
d 20.6, 21.1, 39.7, 41.6, 54.0,
75.1, 76.1, 173.6, 173.9 ppm, IR (KBr): nmax 3054, 2986, 2305, 1758,
1420, 1266 cmꢂ1, HRMS (QTOF ESþ): m/z calcd for C9H13O4:
185.0814; found: 185.0814 [MþH]þ. Compound 14b: mp:
117e118 ꢀC, 1H NMR (400 MHz, CDCl3)
d
1.4 (d, J¼6.1 Hz, 6H), 1.85
(dd, J1¼12.8 Hz, J2¼9.4 Hz, 2H), 2.83 (dd, J1¼12.8 Hz, J2¼5.8 Hz, 2H),
5.02e5.07 (m, 2H) ppm, 13C NMR (100.6 MHz, CDCl3)
d
21.0, 40.6,
18. Singh, R. K. Synthesis 1985, 54.
19. Silverstein, R. M.; Bassler, G. C.; Morrill, T. C. Spectrometric Identification of
54.1, 76.0, 173.6 ppm, IR (KBr): nmax 3058, 2985, 2306, 1757, 1449,
1267 cmꢂ1, compound 14c: mp: 115e118 ꢀC, 1H NMR (400 MHz,
Organic Compounds; John Wiley: New York, NY, 1981; p 189.