H.-B. Chen et al. / Tetrahedron 63 (2007) 2148–2152
2151
855–857; (b) Hoover, T. R.; Imperial, J. P.; Ludden, W.;
Shah, V. K. Biochemistry 1989, 28, 2768–2771; (c) Kim, J.;
Rees, D. C. Science 1992, 257, 1677–1682.
4.1.5. Triethyl per-homocitrate (12).
4.1.5.1. Method 1 (via indium-mediated allylation of 10
followed by subsequent oxidative cleavage and esterifica-
tion). Following the procedure described for the allylation of
5, 11 was synthesized in 86% yield from 10.
3. Zabriskie, T. M.; Jackson, M. D. Nat. Prod. Rep. 2000, 17,
85–97.
4. (a) Suvarna, K.; Seah, L.; Bhattacharjee, V.; Bhattacharjee,
J. K. Curr. Genet. 1998, 33, 268–275; (b) Palmer, D. R. J.;
Balogh, H.; Ma, G.; Zhou, X.; Marko, M.; Kaminskyj,
S. G. W. Pharmazie 2004, 59, 93–98.
5. For racemic synthesis of homocitric acid lactone, see: (a)
Maragoudakis, M. E.; Strassman, M. J. Biol. Chem. 1966,
241, 695–699; (b) Tucci, A. F.; Ceci, L. N.; Bhattacharjee,
J. K. Methods Enzymol. 1969, 13, 619–623; (c) Li, Z.-C.; Xu,
J.-Q. Molecules 1998, 3, 31–34.
6. For a racemic synthesis followed by resolution, see: (a)
Ancliff, R. A.; Russell, A. T.; Sanderson, A. J. Tetrahedron:
Asymmetry 1997, 8, 3379–3382; (b) For chiral synthesis,
see: Thomas, U.; Kalyanpur, M. G.; Stevens, C. M.
Biochemistry 1966, 5, 2513–2516; See also: (c) Tavassoli,
A.; Duffy, J. E. S.; Young, D. W. Tetrahedron Lett. 2005,
46, 2093–2096.
Compound 11: pale yellow oil. IR (film) nmax: 3517, 3073,
2980, 1735, 1637, 1222, 1175 cmꢀ1 1H NMR (CDCl3,
;
400 MHz) d: 5.83–5.70 (m, 1H), 5.16–5.08 (m, 2H), 4.30–
4.21 (m, 2H), 4.13 (q, J¼7.1 Hz, 2H), 3.25 (s, 1H, OH,
D2O exchangeable), 2.48–2.35 (m, 2H), 2.35–2.24 (m,
2H), 1.88–1.77 (m, 2H), 1.74–1.65 (m, 1H), 1.55–1.45 (m,
1H), 1.31 (t, J¼7.1 Hz, 3H), 1.26 (t, J¼7.1 Hz, 3H); 13C
NMR (CDCl3, 100 MHz) d: 175.8, 173.2, 132.2, 119.0,
76.7, 62.0, 60.3, 43.9, 38.0, 34.2, 19.1, 14.3, 14.2. MS
(ESI, m/z): 259 (M+H)+, 281 (M+Na)+. Anal. Calcd for
C13H22O5: C, 60.45; H, 8.58. Found: C, 60.51; H, 8.49.
Compound 12 was prepared in 92% yield from 11 by follow-
ing the procedure described for the synthesis of 7/8.
7. (a) For asymmetric synthesis of homocitric acid lactone, see:
Rodriguez, G. H. R.; Biellmann, J. F. J. Org. Chem. 1996, 61,
1822–1824; (b) Ma, G.; Palmer, D. R. J. Tetrahedron Lett.
2000, 41, 9209–9212; (c) Xu, P.-F.; Matsumoto, T.; Ohki, Y.;
Tatsumi, K. Tetrahedron Lett. 2005, 46, 3815–3818; (d) Paju,
A.; Kanger, T.; Pehk, T.; Eek, M.; Lopp, M. Tetrahedron
2004, 60, 9081–9084; (e) Huang, P.-Q.; Li, Z.-Y.
Tetrahedron: Asymmetry 2005, 16, 3367–3370.
4.1.5.2. Method 2 (via enolate addition to 10). To a solu-
tion of HMDS (0.500 g, 0.65 mL, 3.08 mmol) in 2.0 mL an-
hydrous THF at 0 ꢁC was added dropwise n-BuLi (2.5 M
solution in n-hexane, 2.31 mmol, 0.90 mL). After stirring
for about 30 min, the mixture was cooled to ꢀ78 ꢁC. To
which was added EtOAc (0.65 mL, 2.51 mmol) and the
stirring was continued at ꢀ78 ꢁC for about 30 min. To the re-
sulting mixture was added dropwise 10 (0.33 g, 1.54 mmol)
in 4.50 mL anhydrous THF. The reaction mixture was stirred
at ꢀ78 ꢁC for another 3 h and then quenched with saturated
NH4Cl. The resulting mixture was extracted with diethyl
ether (3ꢂ5 mL). The combined organic layers were dried
over anhydrous Na2SO4, filtered, and concentrated under
reduced pressure. The residue was purified by flash chroma-
tography on silica gel (eluent: EtOAc–PE 1/6) to afford 12
(0.34 g, 1.12 mmol, yield: 72%) as a pale yellow oil. IR
(film) nmax: 3517, 2980, 1735, 1641, 1446, 1372, 1222,
1175, 1025 cmꢀ1; IR (film) nmax: 3508, 2982, 2938, 1739,
8. For an asymmetric synthesis of a precursor of (S)-per-homo-
citric acid, see Ref. 7e.
9. (a) Tsai, K. R.; Wan, H. L. J. Cluster Sci. 1995, 6, 485–501;
(b) Zhou, Z. H.; Wan, H. L.; Tsai, K. R. Inorg. Chem. 2000,
39, 59–64; (c) Zhou, Z. H.; Hou, S. Y.; Cao, Z. X.; Tsai,
K. R.; Chow, Y. L. Inorg. Chem. 2006, 45, 8447–8451.
10. (a) Strassman, M.; Ceci, L. N. Biochem. Biophys. Res.
Commun. 1964, 14, 262–267; (b) Strassman, M.; Ceci, L. N.
J. Biol. Chem. 1965, 240, 4357–4361; (c) Hogg, R. W.;
Broquist, H. P. J. Biol. Chem. 1968, 243, 1839–1845.
11. (a) Loh, T.-P.; Huang, J.-M.; Goh, S.-H.; Vittal, J. J. Org. Lett.
2000, 2, 1291–1294; (b) Nakamura, S.; Sato, H.; Hirata, Y.;
Watanabe, N.; Hashimoto, S. Tetrahedron 2005, 61, 11078–
11106; (c) Roers, R.; Verdine, G. L. Tetrahedron Lett. 2001,
42, 3563–3565.
1736, 1732, 1374, 1183, 1096, 1030 cmꢀ1 1H NMR
;
(CDCl3, 400 MHz) d: 4.32–4.21 (m, 2H), 4.12 (2q, overlap-
ped, each J¼7.0 Hz, 4H), 3.75 (s, 1H, OH, D2O exchange-
able), 2.91 (d, J¼16.2 Hz, 1H), 2.67 (d, J¼16.2 Hz, 1H),
2.36–2.23 (m, 2H), 1.84–1.58 (m, 4H), 1.30 (t, J¼7.0 Hz,
3H), 1.24 (2t, overlapped, each J¼7.0 Hz, 6H); 13C NMR
(100 MHz, CDCl3) d: 174.8, 173.0, 170.6, 74.8, 62.0, 60.8,
60.3, 43.5, 38.4, 34.0, 18.8, 14.2, 14.1, 14.0; MS (ESI,
m/z): 305 (M+H)+, 327 (M+Na)+. Anal. Calcd for
C14H24O7: C, 55.25; H, 7.95. Found: C, 55.15; H, 8.04.
12. Carlsen, P. H. J.; Katsuki, T.; Martin, V. S.; Sharpless, K. B.
J. Org. Chem. 1981, 46, 3936–3938.
13. For allyl metal addition to a-keto-esters or a-keto-amides,
see: (a) Soai, K.; Ishizaki, M. J. Org. Chem. 1986, 51,
3290–3295; (b) Kiegiel, K.; Jurczak, J. Tetrahedron Lett.
1999, 40, 1009–1012; (c) Loh, T.-P.; Huang, J.-M.; Xu,
K.-C.; Goh, S.-H.; Vittal, J. J. Tetrahedron Lett. 2000, 41,
6511–6515; (d) Shin, J. A.; Cha, J. H.; Pae, A. N.; Choi,
K. I.; Koh, H. Y.; Kang, H.-Y.; Cho, Y. S. Tetrahedron Lett.
2001, 42, 5489–5492; (e) Basavaiah, D.; Sreenivasulu, B.
Tetrahedron Lett. 2002, 43, 2987–2990; (f) Kaur, P.; Singh,
P.; Kumar, S. Tetrahedron 2005, 61, 8231–8240; (g) Chen,
J. H.; Venkatesham, U.; Lee, L. C.; Chen, K. M.
Tetrahedron 2006, 62, 887–893.
Acknowledgements
We thank the NSF of China for financial support. Partial
support from the program for Innovative Research Team in
Science and Technology in Fujian Province University is
acknowledged.
References and notes
14. For a review on selective reactions using allylic metals, see:
Yamamoto, Y. Chem. Rev. 1993, 93, 2207–2293.
1. Burgess, B. K.; Lowe, D. J. Chem. Rev. 1996, 96, 2983–3011.
2. (a) Hoover, T. R.; Robertson, A. D.; Cerny, R. L.; Hayes, R. N.;
Imperial, J.; Shah, V. K.; Ludden, P. W. Nature 1987, 329,
15. For reviews, see: (a) Li, C.-J.; Chan, T.-K. Tetrahedron 1999,
55, 1149–1176; (b) Ranu, B. C. Eur. J. Org. Chem. 2000,
2347–2356; (c) Pae, A. M.; Cho, Y.-S. Curr. Org. Chem.