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4.16. Esterification of 1 and 3 with isovaleroyl chloride
4.16.1. Typical procedure. To a 15 mL round bottomed flask under
magnetic stirring previously flame-dried over argon, it was added
(ꢀ)-blastimicinolactol (1) (0.47 mmol; 0.08 g) and pyridine
(10 mL). The mixture was cooled to 0 ꢁC and then isovaleroyl
chloride (2.43 mmol; 0.3 mL) was added. The resulting mixture was
stirred at room temperature for 6 h and then diluted with ethyl
acetate (10 mL), washed with saturated aqueous solution of CuSO4
(2ꢂ20 mL) and brine (10 mL). The organic phase was dried with
magnesium sulfate and the solvents were removed under vacuum.
The residue was purified by flash silica gel column chromatography
eluting with a mixture (9:1) of hexane/ethyl acetate.
€
(b) Petragnani, N.; Stefani, H. A. Tetrahedron 2005, 61, 1613; (c) Zeni, G.; Ludtke,
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17, 2252.
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4.16.1.1. (2S,3R,4R)-4-Butyl-2-methyl-5-oxotetrahydrofuran-3-yl
3-methylbutanoate; (þ)-blastmycinone (2). Colorless liquid (0.12 g,
96%); dH (300 MHz, CDCl3) 0.92 (3H, t, J 7.2 Hz), 0.98 (6H, d, J 6.6 Hz),
1.32e1.49 [(7H, m), 1.47 (3H, d, J 6.6 Hz)], 1.61e1.68 (1H, m),
1.84e1.88 (1H, m), 2.07e2.16 (1H, m), 2.23 (2H, d, J 6.9 Hz), 2.69
(1H, dt, J 8.1, 6.0 Hz), 4.37 (1H, dq, J 6.6, 4.8 Hz), 4.95 (1H, dd, J 6.0,
4.8 Hz); dC (75 MHz, CDCl3) 13.8, 19.5, 22.3, 22.4, 25.7, 28.9, 29.0,
43.2, 46.5, 78.5, 79.4, 172.4, 175.9; nmax (liquid film) 2960, 2874,
11. Naganuma, S.; Sakai, K.; Hasumi, K.; Endo, A. J. Antibiot. 1992, 45, 1216.
12. (a) Mulzer, J.; Salii, N.; Hartl, H. Tetrahedron: Asymmetry 1993, 4, 457; (b) Suzuki,
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1785, 1468, 1181, 1040 cmꢀ1; ½a D22
þ11.8 (c 1.2, CHCl3, ee >97%),
ꢃ
Reddy, V. V. R.; Sharma, G. V. M. Synthesis 2004, 13, 2107.
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lit.15b
½
a 2D0
ꢃ
þ11.0 (c 1.2, CHCl3); chiral GC-FID [SupelcoÒ Beta DEX
110 column (30 mꢂ0.25 mmꢂ0.25
mm), carrier gas: H2, injector
17. Azevedo, M. B. M.; Greene, A. E. J. Org. Chem. 1995, 60, 4940.
18. (a) Inghardt, T.; Frejd, T. Tetrahedron 1991, 47, 6483; (b) Chen, M. J.; Lo, C. Y.;
temperature: 275 ꢁC, detector temperature: 275 ꢁC, pressure:
100 kPa, method: Ti 90 ꢁC (20 min)e1 ꢁC/mineTf 120 ꢁC (100 min)]
tR: ent-(1) 111.404 min and (2) 113.182 min; CAS [27981-25-5].
ꢀ
Chin, C. C.; Liu, R. S. J. Org. Chem. 2000, 65, 6362; (c) Esteve, C.; Ferrero, M.;
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4.16.1.2. (2S,3R,4R)-4-Hexyl-2-methyl-5-oxotetrahydrofuran-3-yl
3-methylbutanoate; (þ)-Antimycinone (4). Colorless liquid (0.13 g,
96%); dH (500 MHz, CDCl3) 0.88 (3H, t, J 7.0 Hz), 0.98 (6H, d, J 7.0 Hz),
1.26e1.45 (8H, m),1.47 (3H, d, J 6.5 Hz),1.59e1.67 (1H, m),1.84e1.89
(1H, m), 2.11e2.15 (1H, m), 2.23 (2H, d, J 7.0 Hz), 2.69 (1H, dt, J 8.5,
5.5 Hz), 4.36 (1H, dq, J 7.0, 5.0 Hz), 4.94 (1H, dd, J 5.5, 5.0 Hz); dC
(125 MHz, CDCl3) 13.9, 19.3, 22.2, 22.4, 25.6, 26.7, 28.8, 29.2, 31.4,
43.0, 46.4, 78.3, 79.3, 172.3, 175.8; nmax (liquid film) 2959, 2872,
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1786, 1743, 1467, 1182, 1120, 1040 cmꢀ1; ½a D20
þ10.1 (c 1.5, CHCl3, ee
ꢃ
>97%), lit.26a
½
a 2D0
ꢃ
þ7.8 (c 1.75, CHCl3); chiral GC-FID [SupelcoÒ Beta
DEX 110 column (30 mꢂ0.25 mmꢂ0.25
mm), carrier gas: H2, in-
jector temperature: 275 ꢁC, detector temperature: 275 ꢁC, pressure:
100 kPa, method: Ti 90 ꢁC (20 min)e1 ꢁC/mineTf 120 ꢁC (100 min)]
tR: ent-(3) 261.365 min and (3) 263.599 min; CAS [132864-91-6].
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Acknowledgements
The authors thank FAPESP, CAPES and CNPq for the financial
support, Amano Pharmaceutical Co. and Novozymes Inc. are ac-
knowledged for their generous gifts of lipases. Alexandre Sardelli
Guarezemini is acknowledged for technical assistance.
ꢀ
Trans. 1 1995, 317; (c) Kurti, L.; Czako, B. Strategic Applications of Named Re-
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Supplementary data
Supplementary data related to this article can be found online at
References and notes
1. (a) Petragnani, N.; Stefani, H. A. Tellurium in Organic Synthesis: Best Synthetic
Methods, 2nd ed.; Academic: London, 2007; (b) Comasseto, J. V.; Clososki, G. C.;
36. Watson, S. C.; Eastham, J. F. J. Organomet. Chem. 1976, 9, 165.