S. P. Panchgalle et al. / Tetrahedron: Asymmetry 21 (2010) 2399–2401
2401
2. (a) Michael, J. P. Nat. Prod. Rep. 2007, 24, 191; (b) Daly, J. W.; Garraffo, H. M.;
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3. For some selected examples, see: (a) Burnett, D. A.; Choi, J.-K.; Hart, D. J.; Tsai,
Y.-M. J. Am. Chem. Soc. 1984, 106, 8201; (b) Pearson, W. H.; Lin, K.-C.
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3099.
4. (a) Hua, D. H.; Bharathi, S. N.; Takusagawa, F.; Tsujimoto, T.; Panangadan, J. A.
K.; Hung, M. H.; Bravo, A. A.; Erpelding, A. M. J. Org. Chem. 1989, 54, 5659; (b)
Waldmann, H.; Braun, M.; Dräger, B. Angew. Chem., Int. Ed. Engl. 1990, 29, 1468;
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M.; Shibasaki, M. Tetrahedron Lett. 1993, 34, 4965; (g) Sato, Y.; Nukui, S.;
Sodeoka, M.; Shibasaki, M. Tetrahedron 1994, 50, 371; (h) Michael, J.;
Munchhof, M. J.; Meyers, A. I. J. Org. Chem. 1995, 60, 7084; (i) Takahata, H.;
Kubota, M.; Takahashi, S.; Momose, T. Tetrahedron: Asymmetry 1996, 7, 3047; (j)
Arisawa, M.; Takezawa, E.; Nishida, A.; Mori, M.; Nakagawa, M. Synlett 1997,
1179; (k) Sánchez-Sancho, F.; Herradón, B. Tetrahedron: Asymmetry 1998, 1951,
9; (l) Davies, S. B.; McKervey, M. A. Tetrahedron Lett. 1999, 40, 1229; (m) Sibi, M.
P.; Christensen, J. W. J. Org. Chem. 1999, 64, 6434; (n) Arisawa, M.; Takahashi,
M.; Takezawa, E.; Yamaguchi, T.; Torisawa, Y.; Nishida, A.; Nakagawa, M. Chem.
Pharm. Bull. 2000, 48, 1593; (o) Michael, D.; Groaning, M. D.; Meyers, A. I. Chem.
Commun. 2000, 1027; (p) Andrés, J. M.; Herráiz-Sierra, I.; Pedrosa, R.; Pérez-
Encabo, A. Eur. J. Org. Chem. 2000, 1719; (q) Costa, A.; Nájera, C.; Sansano, J. M.
Tetrahedron: Asymmetry 2001, 12, 2205; (r) Yoda, H.; Katoh, H.; Ujihara, Y.;
Takabe, K. Tetrahedron Lett. 2001, 42, 2509; (s) Park, S. H.; Kang, H. J.; Ko, S.;
Park, S.; Chang, S. Tetrahedron: Asymmetry 2001, 12, 2621; (t) Dieter, R. K.;
Chen, N.; Watson, R. T. Tetrahedron 2005, 61, 3221; (u) Hjelmgaard, T.;
Gardette, D.; Tanner, D.; Aitken, D. J. Tetrahedron: Asymmetry 2007, 18, 671; (v)
Clive, D. L. J.; Li, Z.; Yu, M. J. Org. Chem. 2007, 72, 5608; (w) Kuhakarn, C.;
Seehasombat, P.; Jaipetch, T.; Pohmakotr, M.; Reutrakul, V. Tetrahedron 2008,
64, 1663; (x) Lebrun, S.; Couture, A.; Deniau, E.; Grandclaudon, P. Synthesis
2008, 2771.
was followed by the addition of lithium bromide (1.300 g, 15 mmol),
triethyl phosphonoacetate (3.360 g, 15 mmol), and DBU (1.520 g,
10 mmol) and the whole mixture was stirred at 5 °C for 45 min. It
was then quenched by the addition of aqueous ammonium chloride
solution and extracted with ethyl acetate (3 ꢂ 200 mL). The com-
bined organic layers were washed with brine, dried over anhydrous
Na2SO4, and concentrated under reduced pressure to give the crude
product 6, whichwas then purified by flash column chromatography
(packed with silica gel 60–120 mesh) using petroleum ether and
ethyl acetate as eluents to afford the pure product 6.
Yield: 3.891 g (76%); viscous liquid; ½a D25
¼ þ17:4 (c 1.0, CHCl3);
ꢃ
ee >99%;18 IR (CHCl3) mmax 3389, 3020, 2926, 2852, 1758, 1715,
1289, 1215, 1041, 757 cmꢀ1 1H NMR (200 MHz, CDCl3): d ppm
;
1.26 (t, J = 7.1 Hz, 3H), 1.60–1.73 (m, 5H), 2.31 (t, J = 6.9 Hz, 2H),
3.64 (s, 3H), 4.14–4.19 (q, J = 7.1 Hz, 2H), 4.69–4.83 (m, 1H), 5.16
(m, 4H), 5.91 (br s, 1H), 6.60 (d, J = 15.5 Hz, 1H), 6.81–6.86 (m,
1H), 7.31 (m, 10H); 13C NMR (50 MHz, CDCl3): d = 14.0, 21.0,
30.0, 33.2, 51.4, 58.1, 60.4, 67.5, 122.9, 127.7, 128.0, 128.1, 128.3,
135.4, 144.4, 155.5, 156.4, 166.0, 173.7 ppm; Elemental Anal. Calcd
for C27H32N2O8: C, 63.27; H, 6.29; N, 5.47. Found: C, 63.31; H, 6.19;
N, 5.41. LC–MS: m/z = 535.43 (M++Na).
4.4. (R)-Hexahydroindolizine-3,5-dione 10
A solution of 6 (2.0 g, 3.90 mmol) in MeOH (50 mL) and acetic
acid (10 drops) was treated with Raney nickel (5 g, excess) under
an H2 (80 psig) atmosphere for 24 h. The reaction mixture was fil-
tered over Celite and concentrated to give the crude c-amino ester
which on stirring in EtOH in the presence of catalytic pyridine at
50 °C for 5 h cyclized to product 10 (purified by flash chromatogra-
phy (SiO2) using ethyl acetate as eluent).
5. (a) Dalko, P. I.; Moisan, L. Angew. Chem., Int. Ed. 2001, 40, 3726; (b) Dalko, P. I.;
Moisan, L. Angew. Chem., Int. Ed. 2004, 43, 5138; (c) Houk, K. N., List, B. (Eds.).
Acc. Chem. Res. 2004, 37, 487.; (d) List, B., Bolm, C. (Eds.). Adv. Synth. Catal. 2004,
346.; (e) List, B.; Seayad, J. Org. Biomol. Chem. 2005, 3, 719.
Yield: 0.484 g (81%); viscous liquid; ½a D25
ꢃ
¼ þ26:1 (c 1.0, CHCl3);
IR (CHCl3) mmax 2918, 2854, 1668, 1461, 1377, 1112, 721 cmꢀ1
;
1H
6. List, B. Tetrahedron 2002, 58, 5573.
7. (a) List, B. J. Am. Chem. Soc. 2002, 125, 5656; (b) Bogevig, A.; Juhl, K.;
Kumaragurubaran, N.; Zhuang, W.; Jorgensen, K. A. Angew. Chem., Int. Ed. 2002,
41, 1790; (c) Kumaragurubaran, N.; Juhl, K.; Zhuang, W.; Bogevig, A.; Jorgensen,
K. A. J. Am. Chem. Soc. 2002, 124, 6254; (d) Vogt, H.; Vanderheiden, S.; Brase, S.
Chem. Commun. 2003, 2448; (e) Iwamura, H.; Mathew, S. P.; Blackmond, D. G. J.
Am. Chem. Soc. 2004, 126, 11770.
NMR (200 MHz, CDCl3): d ppm 1.37–1.47 (m, 4H), 1.86–1.95 (m,
2H), 2.32 (t, J = 8.6 Hz, 2H), 2.40–2.61 (m, 2H), 3.55–3.61 (m, 1H);
13C NMR (50 MHz, CDCl3): d = 19.5, 22.5, 27.8, 30.4, 33.2, 55.2,
172.7, 174.5 ppm.
8. (a) Chowdari, N. S.; Ramachary, D. B.; Barbas, C. F., III Org. Lett. 2003, 5, 1685;
(b) Zhong, G. Chem. Commun. 2004, 606; (c) Zhong, G.; Yu, Y. Org. Lett. 2004,
6, 1637; (d) Mangion, I. K.; MacMillan, D. W. C. J. Am. Chem. Soc. 2005, 127,
3696; (e) Kumaran, S.; Shaw, D. M.; Longbottom, D. A.; Ley, S. V. Org. Lett.
2005, 7, 4189; (f) Kotkar, S. P.; Chavan, V. B.; Sudalai, A. Org. Lett. 2007, 9,
1001.
9. (a) Fusetani, N.; Matsunaga, S.; Matsumoto, H.; Takebayashi, Y. J. Am. Chem. Soc.
1990, 112, 7053; (b) Coleman, J. E.; de Silva, E. D.; Kong, F.; Andersen, R. J.;
Allen, T. M. Tetrahedron 1995, 51, 10653.
10. (a) Thoen, J. C.; Morales-Ramos, A. I.; Lipton, M. A. Org. Lett. 2002, 4, 4455; (b)
Palomo, C.; Oiarbide, M.; Landa, A.; Esnal, A.; Linden, A. J. Org. Chem. 2001, 66,
4180; (c) Broady, S. D.; Rexhausen, J. E.; Thomas, E. J. J. Chem. Soc., Perkin Trans.
1 1999, 1083.
11. Hulme, A. N.; Montgomery, C. H. Tetrahedron Lett. 2003, 44, 7649.
12. (a) Oba, M.; Koguchi, S.; Nishiyama, K. Tetrahedron 2002, 58, 9359; (b) Dauban,
P.; Saint-Fuscien, C. D.; Acher, F.; Prezeau, L.; Brabet, I.; Pin, J.; Dodd, R. H.
Bioorg. Med. Chem. Lett. 2000, 10, 129; (c) Dauban, P.; Saint-Fuscien, C. D.; Dodd,
R. H. Tetrahedron 1999, 55, 7589.
4.5. (R)-(ꢀ)-Coniceine 2
To a solution of bicyclic lactam 10 (0.306 g, 2 mmol) in THF
(15 mL) under an argon atmosphere were added BF3ꢁEt2O
(0.282 g, 2 mmol, 1 equiv) and boron-dimethyl sulfide (0.304 g,
4 mmol, 2 equiv) dropwise. Once H2 evolution stopped, the solu-
tion was refluxed for 24 h. The solution was concentrated under re-
duced pressure and the residue was purified by flash column
chromatography (SiO2) to give (R)-(ꢀ)-coniceine 2.
Yield: 0.217 g (87%); viscous liquid; ½a D25
¼ ꢀ10:0 (c 1.24, EtOH)
ꢃ
{Lit.4x
½
a 2D5
ꢃ
¼ ꢀ9:8 (c 1.10, EtOH)}; IR (CHCl3) mmax 2952, 2920,
1461, 1454, 1320,1255, 1096 cmꢀ1 1H NMR (200 MHz, CDCl3): d
;
ppm 1.20–1.42 (m, 11H), 1.95 (dt, J = 3.6, 11.2 Hz, 1H), 2.07 (q,
J = 9.0 Hz, 1H); 3.02–3.13 (m, 2H); 13C NMR (50 MHz, CDCl3):
d = 20.5, 24.5, 25.4, 30.5, 31.0, 53.0, 54.2, 64.3 ppm. Elemental Anal.
Calcd for C8H15N: C, 76.74; H, 12.07; N, 11.19. Found: C, 76.77; H,
12.01; N, 11.07.
13. (a) Wei, Z.-Y.; Knaus, E. E. Tetrahedron 1994, 50, 5569; (b) Wei, Z.-Y.; Knaus, E.
E. Tetrahedron Lett. 1994, 35, 2305; (c) Rubsam, F.; Evers, A. M.; Michel, C.;
Giannis, A. Tetrahedron 1997, 53, 1707; (d) Koskinen, A. M. P.; Otsomaa, L. A.
Tetrahedron 1997, 53, 6473.
14. (a) Jurczak, J.; Golebiowski, A. Chem. Rev. 1989, 89, 149; (b) Gryko, D.; Chalko,
J.; Jurczak, J. Chirality 2003, 514.
15. (a) Fehrentz, J. A.; Castro, B. Synthesis 1983, 676; (b) Rettle, K. E.; Homnick, C. F.;
Ponticello, G. S.; Evans, B. E. J. Org. Chem. 1982, 47, 3016; (c) Lubell, W. D.;
Rapoport, H. J. Am. Chem. Soc. 1988, 110, 7447.
16. Panchgalle, S. P.; Gore, R. G.; Chavan, S. P.; Kalkote, U. R. Tetrahedron:
Asymmetry 1767, 2009, 20; (b) Panchgalle, S. P.; Jogdand, G. F.; Chavan, S. P.;
Kalkote, U. R. Tetrahedron Lett. 2010, 51, 3587; (c) Panchgalle, S. P.; Kunte, S. S.;
Chavan, S. P.; Kalkote, U. R. Synth. Commun. 2010, 40, in press.
Acknowledgment
S.P.P. thanks the University Grants Commission (UGC), New
Delhi, India, for the financial assistance in the form of fellowship.
References
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petroleum ether 2.5:97.5; flow rate: 0.7 mL/min, tR = 87.44 min, tS = 99.49 min.
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