1006
R. N. Kumar, H. M. Meshram / Tetrahedron Letters 52 (2011) 1003–1007
2925, 2855, 1736, 1503, 1454, 1420, 1372, 1259, 1162, 1082, 800, 759,
of diospongin A and cryptofolione are 38.9% and 10.8%, respec-
tively. The intermediates generated in this protocol may be useful
in the total synthesis of related biologically active compounds.
701 cmꢀ1 1H NMR (300 MHz, CDCl3): d 2.91 (dd, J = 8.9, 3.6 Hz, 2H), 3.45 (s,
;
2H), 3.73 (s, 3H), 5.16 (dd, J = 8.9, 3.6 Hz, 1H), 7.22–7.40 (m, 5H); 13C NMR
(75 MHz, CDCl3): d 47.1, 49.7, 51.6, 69.8, 125.6, 127.8, 128.6, 136.4, 166.9,
202.6; ESI-MS: m/z = 245 (M++Na); ESI-HRMS: m/z calcd for C14H16O4Na:
245.0790, found: 245.0793.
Acknowledgment
Spectral and analytical data of 13: ½a D25
ꢁ
+13.8 (c 1, CHCl3); IR (neat): mmax 3450,
3024, 2937, 2861, 1728, 1638, 1576, 1454, 1372, 1259, 1165, 1037, 952,
752 cmꢀ1 1H NMR (300 MHz, CDCl3): d 1.28 (t, J = 6.8 Hz, 3H), 2.81 (d, J = 6.0,
;
R.N.K. thanks Council of Scientific and Industrial research(CSIR),
New Delhi, for the financial assistance in the form of research
fellowships.
2H), 3.45 (s, 2H), 4.18 (q, J = 7.6 Hz, 2H), 4.74 (m, 1H), 6.15 (dd, J = 15.9, 6.0 Hz,
1H), 6.60 (d, J = 15.9 Hz, 1H), 7.16–7.35 (m, 5H); 13C NMR (75 MHz, CDCl3): d
14.1, 49.6, 50.0, 61.6, 68.4, 126.5, 127.8, 128.6, 129.9, 130.6, 136.4, 167.0,
202.7; ESI-MS: m/z = 285 (M++Na); ESI-HRMS: m/z calcd for C14H16O4Na:
285.1103, found: 285.1109.
References and notes
17. Soriente, A.; Rosa, M. D.; Villano, R.; Scettri, A. Tetrahedron: Asymmetry 2000,
11, 2255; (b) Soriente, A.; Rosa, M. D.; Stanzione, M.; Villano, R.; Scettri, A.
Tetrahedron: Asymmetry 2001, 12, 959; (c) Villano, R.; Acocella, M. R.; Rosa, M.
D.; Soriente, A.; Scettri, A. Tetrahedron: Asymmetry 2004, 15, 2421; (d) Xu, Q.;
Yu, J.; Han, F.; Hu, J.; Chen, W.; Yang, L. Tetrahedron: Asymmetry 2010, 21, 156.
18. (a) Gensler, W. J.; Johnson, F.; Sloan, A. D. B. J. Am. Chem. Soc. 1960, 82, 6074; (b)
Crabbe, P.; Garcia, G. A.; Rius, C. J. Chem. Soc., Perkin Trans. I 1973, 810.
19. (a) Narasaka, K.; Pai, F. C. Tetrahedron 1984, 40, 2233; (b) Nakata, T.; Tani, Y.;
Hatozaki, M.; Oishi, T. Chem. Pharm. Bull. 1984, 32, 1411; (c) Prasad, K.; Kepid,
O. Tetrahedron Lett. 1984, 25, 4889.
1. (a) Kadota, S.; Tezuka, Y.; Prasaim, J. K.; Ali, M. S.; Banskota, A. H. Curr. Top. Med.
Chem. 2003, 3, 203; (b) Claeson, P.; Claeson, U. P.; Tuchinda, P.; Rentrakul, V.
Stud. Nat. Prod. Chem. 2002, 26, 881; (c) Zhu, J.; Islas-Gonzales, G.; Bois-
Choussy, M. Org. Prep. Proced. Int. 2000, 32, 505.
2. (a) Palwinder, S.; Bhardwaj, A. J. Med. Chem. 2010, 53, 3707; (b) Aggarwal, B. B.;
Kumar, A.; Bharati, A. C. Anticancer Res. 2003, 23, 363; (c) Ishida, J.; Kozuka, M.;
Tokuda, H.; Nishino, H.; Nagumo, S.; Lee, K. H.; Nagai, M. Bioorg. Med. Chem.
2002, 10, 3361.
3. (a) Kang, G.; Kong, P. J.; Yuh, S. V.; Chun, W.; Kim, S. S. J. Pharmacol. Sci. 2004, 94,
325; (b) Yadav, P. N.; Liu, Z.; Rafi, M. M. J. Pharmacol. Exp. Ther. 2003, 305, 925.
4. (a) Balasubramanyam, M.; Koteswari, A. Q. A.; Kumar, R. S.; Monickaraj, S. F.;
Maheawari, J. U.; Mohan, V. J. Biosci. 2003, 28, 15; (b) Mohamad, H.; Lajis, N. H.;
Abas, F.; Ali, A. M.; Sukari, M. A.; Kikuzaki, H.; Nakatani, N. J. Nat. Prod. 2005, 68,
285.
20. Spectral and analytical data of 7: ½a D25
ꢀ52.5 (c 1, CHCl3); IR (neat): mmax 3081,
ꢁ
2922, 2853, 1740, 1640, 1539, 1459, 1378, 1259, 1201, 1164, 965, 799, 701,
536 cmꢀ1 1H NMR (300 MHz, CDCl3): d 1.37 (dt, J = 13.5, 2.9 Hz, 1H), 1.40 (s,
;
3H), 1.50 (s, 3H), 1.74 (dt, J = 13.5, 2.9 Hz, 1H), 2.31 (dd, J = 15.4, 5.8 Hz, 1H),
2.50 (dd, J = 15.4, 6.7 Hz, 1H), 3.60 (s, 3H) 4.33–4.41 (m, 1H), 4.84 (dd, J = 11.5,
1.9 Hz, 1H), 7.13–7.30 (m, 5H); 13C NMR (75 MHz, CDCl3): d 19.73, 30.17, 38.84,
41.14, 51.70, 66.12, 71.33, 99.35, 125.91, 127.69, 128.47, 142.05, 171.35; ESI-
MS: m/z = 287 (M++Na); ESI-HRMS: m/z calcd for C15H20NaO4: 287.1259,
found: 287.1260.
5. Yin, J.; Kouda, K.; Tezuka, Y.; Le Tran, Q.; Miyahara, T.; Chen, Y.; Kadota, S.
Planta Med. 2004, 70, 54.
6. For the synthesis of diospongin A, see the following: (a) Chandrasekhar, S.;
Shyamsunder, T.; Prakash, S. J.; Prabhakar, A.; Jagadeesh, B. Tetrahedron Lett.
2006, 47, 47; (b) Sawant, K. B.; Jennings, M. P. J. Org. Chem. 2006, 71, 7911; (c)
Bressy, C.; Allais, F.; Cossy, J. Synlett 2006, 3455; (d) Bates, R. W.; Song, P.
Tetrahedron 2007, 63, 4497; (e) Hiebel, M. A.; Pelotier, B.; Piva, O. Tetrahedron
2007, 63, 7874; (f) Kawai, N.; Hande, S. M.; Uenishi, J. Tetrahedron 2007, 63,
9049; (g) Yadav, J. S.; Padmavani, B.; Reddy, B. V. S.; Venugopal, C.; Rao, A. B.
Synlett 2007, 2045; (h) Wang, H.; Shuhler, B. J.; Xian, M. Synlett 2008, 2651; (i)
Sabitha, G.; Padmaja, P.; Yadav, J. S. Helv. Chim. Acta 2008, 91, 2235; (j)
Kumaraswamy, G.; Ramakrishna, G.; Naresh, P.; Jagadeesh, B.; Sridhar, B. J. Org.
Chem. 2009, 74, 8468; (k) Lee, K.; Kim, H.; Hong, J. Org. Lett. 2009, 11, 5202; (l)
More, J. D. Synthesis 2010, 14, 2419.
7. Drewes, S. E.; Sehlapelo, B. M.; Scott-Shaw, R. Phytochemistry 1994, 37, 847.
8. (a) Cavalheiro, A. J.; Yoshida, M. Phytochemistry 2000, 53, 811; (b) Fang, X.;
Anderson, J. E.; Chang, C.; Fanwick, P. E.; McLaughlin, J. L. J. Chem. Soc., Perkin
Trans. I 1990, 1655; (c) Fu, X.; Seavenet, T.; Hadi, A.; Remy, F.; Paoes, M.
Phytochemistry 1993, 33, 1272.
9. Schmeda-Hirschmann, G.; Astudillo, L.; Bastida, J.; Codina, C.; De Arias, A. R.;
Ferreira, M. E.; Inchaustti, A.; Yaluff, G. J. Pharm. Pharmacol. 2001, 53, 563.
10. Sturgeon, C. M.; Cinel, B.; Diaz-Marrero, A. R.; McHardy, L. M.; Ngo, M.;
Andersen, R. J.; Roberge, M. Cancer Chemother. Pharmacol. 2008, 61, 407.
11. For the synthesis of cryptofolione, see the following: (a) Matsuoka, Y.; Aikawa,
K.; Irie, R.; Katsuki, T. Heterocycles 2005, 66, 187; (b) Sabitha, G.; Reddy, S. S. S.;
Reddy, D. V.; Bhaskar, V.; Yadav, J. S. Synthesis 2010, 20, 3453.
12. (a) Tian, X.; Jaber, J. J.; Rychnovsky, S. D. J. Org. Chem. 2006, 71, 3176; (b) Ko, H.
M.; Lee, D. G.; Kim, M. A.; Kim, H. J.; Park, J.; Lah, M. S.; Lee, E. Org. Lett. 2007, 9,
141; (c) Clarke, P. A.; Santos, S. Eur. J. Org. Chem. 2006, 2045; (d) Jasti, R.;
Rychnovsky, S. D. J. Am. Chem. Soc. 2006, 128, 13640.
21. (a) Rychnovsky, S. D.; Skalitzky, D. J. Tetrahedron Lett. 1990, 31, 945; (b)
Rychnovsky, S. D.; Rogers, B.; Yang, G. J. Org. Chem. 1993, 58, 3511; (c) Evans, D.
A.; Rieger, D. L.; Gage, J. R. Tetrahedron Lett. 1990, 31, 7099.
22. Spectral and analytical data of 10: ½a D25
ꢀ41.3 (c 1, CHCl3); IR (neat): mmax 3011,
ꢁ
2921, 2852, 1733, 1641, 1581, 1459, 1377, 1201, 1137, 1024, 760, 696 cmꢀ1
;
1H NMR (300 MHz, CDCl3): d 1.40 (dt, J = 12.8, 7.5 Hz, 1H), 1.43 (s, 3H), 1.50 (s,
3H), 1.72–1.71 (dt, J = 12.8, 2.7 Hz, 1H), 2.38 (dd, J = 15.1, 6.8 Hz, 1H), 2.50 (dd,
J = 14.4, 6.8 Hz, 1H), 4.11 (m, 1H), 4.82 (dd, J = 11.3, 2.3 Hz, 1H), 6.90 (d,
J = 15.9 Hz, 1H), 7.01 (dt, J = 15.9, 8.10 Hz, 1H), 7.13–7.31 (m, 5H), 7.39 (t,
J = 7.5 Hz, 2H) 7.47 (t, J = 6.79 Hz, 1H), 7.85 (d, J = 8.10 Hz, 2H); 13C NMR
(75 MHz, CDCl3): d 18.69, 29.16, 38.14, 38.61, 67.07, 70.20, 95.05, 124.70,
126.45, 126.84, 127.24, 127.35, 127.47, 131.49, 136.71, 141.01, 143.25, 188.63;
ESI-MS: m/z = 359 (M++Na); ESI-HRMS: m/z calcd for C22H24NaO3: 359.1623,
found: 359.1639.
23. Spectral and analytical data of 1: mp 102–105 °C. ½a D25
ꢀ23.1 (c 0.9, CHCl3); IR
ꢁ
(neat): mmax 3375, 2923, 2855, 1688, 1590, 1450, 1258, 1060, 919, 750, 694,
534 cmꢀ1 1H NMR (300 MHz, CDCl3): d 1.58–1.79 (m, 2H), 1.91–1.98 (m, 2H),
;
3.07 (dd, J = 15.86, 6.80 Hz, 1H), 3.41 (dd, J = 15.86, 6.01 Hz, 1H), 4.38 (t,
J = 3.02 Hz, 1H) 4.65 (m, 1H), 4.94 (dd, J = 11.33, 1,51 Hz, 1H), 7.19–7.37 (m,
5H), 7.52 (t, J = 7.55 Hz, 2H) 7.68 (t, J = 6.04 Hz, 1H) 7.91 (d, J = 6.80 Hz, 2H); 13
C
NMR (75 MHz, CDCl3): d 38.67, 40.29, 45.17, 64.66, 69.06, 73.85, 125.82,
127.20, 128.22, 128.44, 128.53, 133.03, 142.78, 197.89; ESI-MS: m/z = 319
(M++Na); ESI-HRMS: m/z calcd for C19H20NaO3: 319.1310, found: 319.1315.
24. (a) Evans, D. A.; Chapman, K. T.; Carreira, E. M. J. Am. Chem. Soc. 1988, 110,
3560; (b) Evans, D. A.; Chapman, K. T. Tetrahedron Lett. 1986, 27, 5939.
25. Spectral and analytical data of 15: ½a D25
ꢀ19.6 (c 0.6, CHCl3); IR (neat): mmax
ꢁ
3220, 2983, 2863, 1738, 1638, 1592, 1510, 1468, 1378, 1327, 1232, 1021, 984,
13. (a) Crimmins, M. T.; Smith, A. C. Org. Lett. 2006, 9, 1003; (b) Gademann, K.;
Bethuel, Y. Org. Lett. 2004, 6, 4707; (c) Gademann, K.; Bethuel, Y. Angew. Chem.,
Int. Ed. 2004, 116, 3389; (d) Snider, B. B.; Song, F. Org. Lett. 2001, 3, 1817; (e)
Fettes, A.; Carreira, E. M. J. Org. Chem. 2003, 68, 9274; (f) Sabitha, G.; Bhaskar,
V.; Reddy, S. S. S.; Yadav, J. S. Tetrahedron 2008, 64, 10207; For a review see: (g)
Soriente, A.; De Rosa, M.; Villano, R.; Scettri, A. Curr. Org. Chem. 2004, 8, 993.
14. (a) Reddy, B. C.; Meshram, H. M. Tetrahedron Lett. 2010, 51, 4020; (b) Prasad, B.
R. V.; Meshram, H. M. Tetrahedron: Asymmetry 2010, 21, 1837.
769, 634 cmꢀ1 1H NMR (300 MHz, CDCl3): d 1.28 (t, J = 6.8 Hz, 3H), 1.38 (s, 3H),
;
1.41 (s, 3H), 1.77 (ddd, J = 9.8, 6.8, 6.1 Hz, 1H), 1.92 (ddd, J = 9.8, 6.8, 6.1 Hz,
1H), 2.41 (dd, J = 15.1, 6.1 Hz, 1H), 2.53 (dd, J = 15.1, 7.6 Hz, 1H), 4.14 (q,
J = 7.5 Hz, 2H) 4.32 (m, 1H), 4.48 (m, 1H), 6.17 (dd, J = 15.9, 6.0 Hz, 1H), 6.52 (d,
J = 15.9 Hz, 1H), 7.15–7.38 (m, 5H); 13C NMR (75 MHz, CDCl3): d 14.1, 24.5,
25.2, 37.2, 40.8, 60.4, 63.2, 67.5, 100.6, 126.4, 127.6, 128.4, 129.4, 130.5, 136.5,
170.8; ESI-MS: m/z = 327 (M++Na); ESI-HRMS: m/z calcd for C18H24NaO4:
327.1572, found: 327.1587.
15. Brownbridge, P.; Chan, T. H.; Brook, M. A.; Kang, G. J. Can. J. Chem. 1983, 61, 688.
26. (a) Hanawa, H.; Hashimoto, T.; Maruoka, K. J. Am. Chem. Soc. 2003, 125, 1708;
(b) Hanawa, H.; Uraguchi, D.; Konishi, S.; Hashimoto, T.; Maruoka, K. Chem. Eur.
J. 2003, 9, 4405.
16. General procedure for the synthesis of 5:
A mixture of Ti(OiPr)4 (568 mg,
2 mmol), (S)-BINOL (572 mg, 2 mmol) and 4 Å molecular sieves (3 g) in THF
(20 mL) was stirred at rt for 1 h. Then the mixture was cooled to ꢀ78 °C and
27. Spectral and analytical data of 19: ½a D25
ꢁ
+40.8 (c 1, CHCl3); IR (neat): mmax 3440,
benzaldehyde
3 (2.12 g, 20 mmol) was added dropwise followed by the
2927, 2873, 1678, 1621, 1549, 1459, 1373, 1288, 1172, 1024, 790, 658 cmꢀ1
;
addition of silyloxydiene
4 (8.6 ml 40 mmol) over 30 min. The resulting
1H NMR (300 MHz, CDCl3): d 1.36 (s, 3H), 1.4 (s, 3H), 1.69–1.87 (m, 2H), 2.20–
2.36 (m, 4H), 3.91 (m, 1H), 4.11 (dt, J = 6.2, 5.8 Hz, 1H), 4.47 (dt, J = 7.9, 5.8 Hz,
1H), 5.10 (m, 1H), 5.13 (dd, J = 5.48, 2.0 Hz, 1H), 5.56 (dd, J = 15.5, 5.7 Hz, 1H),
5.65 (dt, J = 15.5, 6.2 Hz, 1H), 5.72–5.86 (m, 1H), 6.17 (dd, J = 16.2, 6.0 Hz, 1H),
6.51 (d, J = 16.2 Hz, 1H), 7.09–7.39 (m, 5H); 13C NMR (75 MHz, CDCl3): d 24.6,
25.3, 37.4, 38.5, 41.2, 65.0, 67.4, 78.4, 100.7, 114.3, 126.4, 127.7, 128.5, 129.2,
130.6, 130.9, 131.5, 134.6, 136.4; ESI-MS: m/z = 351 (M++Na); ESI-HRMS: m/z
calcd for C21H28NaO3: 351.1936, found: 351.1945.
solution was stirred under an inert gas atmosphere at ꢀ78 °C for 2 h. It was
allowed to attain rt and stirring was continued overnight. The progress of the
reaction was monitored by TLC. Upon completion of reaction the mixture was
cooled to ꢀ78 °C and then TFA (0.4 mL) was added. The solution was warmed
to rt and stirring was continued for 1 h. After ensuring the completion of
desilylation, the reaction mixture was diluted with ether and neutralized by
the dropwise addition of saturated aqueous NaHCO3 solution (2 mL). The
mixture was stirred until the evolution of gas ceased (30 min). The organic
layer was washed with brine, dried over MgSO4 and concentrated in vacuo to
afford a yellow oil. Purification by chromatography on silica gel (30% EtOAc/
hexane) afforded the aldol adduct 5 as a pale yellow oil.
28. (a) Grubbs, R. H.; Chang, S. Tetrahedron 1998, 54, 4413; (b) Grubbs, R. H.
Tetrahedron 2004, 60, 7117.
29. Spectral and analytical data of 21: ½a D25
ꢁ
+62.3 (c 1, CHCl3); IR (neat): mmax 3044,
2973, 2896, 1727, 1646, 1630, 1581, 1534, 1450, 1431, 1365, 1321, 1160, 1124,
Spectral and analytical data of 5: ½a D25
ꢀ56.3 (c 1, CHCl3); IR (neat): mmax 3418,
ꢁ
972, 572 cmꢀ1 1H NMR (300 MHz, CDCl3): d 1.38 (s, 3H), 1.40 (s, 3H), 1.68–
;