Y.-T. He et al. / Tetrahedron 58 (2002) 8805–8810
8809
was then diluted with water (10 mL), and extracted with
EtOAc. The combined organic layers were dried over
anhydrous Na2SO4, concentrated under reduced pressure,
and chromatographed to afford 11 as a white solid (209 mg,
91%). This material was further crystallized from CH2Cl2/
hexanes to give a white crystalline solid (149 mg, 65%). mp
58–608C. IR: 3493, 3427, 3296, 2936, 2919, 2850, 2118,
1 atm of hydrogen at rt for 45 min, the mixture was filtered
and the filtrate was concentrated in vacuo and chromato-
graphed to give 3 as a white solid (36.3 mg, 88%). Method
B: To a mixture of b-hydroxylated lactones 12 (20 mg,
0.071 mmol) and Et3N (6 equiv.) in CH2Cl2 was added
(CF3CO)2O (3.0 equiv.) at 08C. The reaction mixture was
stirred at 08C for 10 h and then warmed to rt for additional
2 h. The reaction mixture was diluted with ether, washed
with water and brine, dried (Na2SO4) and concentrated
under reduced pressure. The crude product was purified by
flash column chromatography to afford 3 (17.2 mg, 92%) as
a white solid. mp: 22–238C. HPLC: 93.9% ee (tR 16.54 min
for (S)-3, and tR 18.05 min for (R)-3); [a]D¼þ33.4 (CHCl3,
c 0.285) [lit.3 [a]D¼þ80 (CHCl3, 0.0028)]; IR: 2928, 2856,
1
1732 cm21. H NMR (CDCl3, 300 MHz): 4.62 (m, 0.5H,
MeCHOCvO), 4.44 (m, 0.5H, MeCHOCvO), 4.31 (m,
0.5H, CHOH), 4.20 (m, 0.5H, CHOH), 2.55 (m, 1H,
CHCvO), 2.18 (td, J¼6.3, 2.4 Hz, 2H, uCCH2), 1.93 (t,
J¼2.7 Hz, 1H, CHu), 1.43 (d, J¼6.0 Hz, 1.5H, CHMe),
1.42 (d, J¼6.6 Hz, 1.5H, CHMe), 1.28–1.70 (m, 18H) ppm.
EIMS (m/z, %): 281 (Mþþ1, 0.87), 264 (Mþþ1–15, 0.41),
116 (100), 111 (32), 99 (74), 81 (43), 67 (39), 57 (77), 55
(43), 41 (4). Anal. calcd for C17H28O3: C, 72.82; H, 10.07.
Found: C, 72.61; H, 10.11.
1759, 1641 cm21
.
1H NMR (CDCl3): 7.00 (dd, J¼3.3,
1.5 Hz, 1H), 5.82 (ddt, J¼16.5, 10.5, 6.8 Hz, 1H), 5.01 (m,
1H), 4.90–5.00 (m, 2H), 2.28 (tdd, J¼7.8, 1.8, 1.5 Hz, 2H),
2.04 (tddd, J¼7.2, 6.8, 1.2, 1.5 Hz, 2H), 1.55 (m, 2H), 1.41
(d, J¼6.6 Hz, 3H), 1.28 (brm, 14H) ppm. 13C NMR (CDCl3,
75 MHz): 172.96, 147.8, 138.21, 133.35, 113.08, 76.36,
32.79, 28.530, 28.49, 28.45, 28.29, 28.17, 28.11, 27.93,
26.41, 24.18, 18.20 ppm. EIMS (m/z, %): 265 (Mþþ1, 6),
264 (Mþ, 5), 246 (1), 235 (3), 219 (2), 207 (4), 193 (5), 179
(7), 169 (6), 152 (9), 137 (13), 123 (17), 112 (37), 109 (25),
95 (42), 81 (43), 67 (44), 57 (100). HRMS (EI) m/z calcd for
C17H28O2 (M)þ: 264.2089. Found: 264.2092.
4.1.8. (4S,5S)-3-(12-Dodecene)-4-hydroxy-5-methyl-
tetrahydro-2-furanone (12). To a solution of alkyne 11
(100 mg, 0.357 mmol) in EtOAc (10 mL) were added
Lindlar catalyst (10 mg) and one drop of quinoline. After
being stirred under 1 atm of hydrogen at rt for 45 min
(monitored by TLC), the mixture was filtered and
concentrated in vacuo and chromatographed eluting with
hexane/diethyl ether (1/1) to give 12 (99 mg, 98%) as a
white solid. mp 43–448C. IR: 3404, 2924, 2850, 1737,
1643, 1465, 1187 cm21. 1H NMR (CDCl3, 300 MHz): 5.82
(ddt, J¼16.5, 10.5, 6.6 Hz, 1H, vCHCH2), 4.98 (m, 1H,
CH2vCHCH2), 4.92 (m, 1H, CH2vCHCH2), 4.63 (qd,
J¼6.3, 5.0 Hz, 0.5H, MeCHOCvO), 4.45 (qd, J¼6.6,
5.1 Hz, 0.5H, MeCHOCvO), 4.32 (dt, J¼4.8, 5.0 Hz, 0.5H,
CHOH), 4.19 (dt, J¼4.8, 5.1 Hz, 0.5H, CHOH), 2.56 (m,
1H, CHCvO), 2.34 (d, J¼4.8 Hz, 1H, CHOH), 2.04 (m,
2H, CH2vCHCH2), 1.44 (d, J¼6.6 Hz, 1.5H, CHMe), 1.40
(d, J¼6.3 Hz, 1.5H, CHMe), 1.27–1.50 (brm, 18H) ppm.
EIMS (m/z, %): 282 (Mþ, 1), 267 (0.4), 265 (2), 129 (33),
116 (82), 111 (35), 99 (56), 67 (26), 57 (100), 55 (54), 41
(56). Anal. calcd for C17H30O3: C, 72.30; H, 10.71. Found:
C, 72.12; H, 10.42.
Acknowledgements
The Major State Basic Research and Development Program
(G2000077500), the Chinese Academy of Sciences and
Shanghai Municipal Commission of Science and Tech-
nology are appreciated for the financial support.
References
1. A recent review see: Alali, F. Q.; Liu, X.-X.; McLaughlin, J. L.
J. Nat. Prod. 1999, 62, 504.
2. Gerber, N. G. Tetrahedron Lett. 1973, 771.
4.1.9. (1)-(5S)-3-(12-Dodecyne)-5-methyl-2(5H)-fura-
none (2). The procedure was followed as that of 1. For
compound 2 (59 mg, 94%): mp 24–258C; HPLC: 91.9% ee
(tR 25.01 min for (S)-2, and tR 30.18 min for (R)-2); [a]D¼
þ30.3 (CHCl3, c 0.46), [lit.3 [a]D¼þ38 (CHCl3, c 0.0026)];
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IR: 3310, 2981, 2930, 2856, 2118, 1756, 1656, 1320 cm21
;
1H NMR (CDCl3, 300 MHz): 6.99 (dd, J¼3.3, 1.8 Hz, 1H),
5.00 (qdd, J¼6.6, 3.3, 1.8 Hz, 1H), 2.27 (tdd, J¼6.9, 1.8,
1.8 Hz, 2H), 2.18 (td, J¼6.9, 2.7 Hz, 2H), 1.94 (t, J¼2.7 Hz,
1H), 1.48–1.57 (m, 4H), 1.41 (d, J¼6.6 Hz, 3H), 1.26–1.43
(brm, 12H) ppm. 13C NMR (CDCl3, 75 MHz): 171.91,
148.88, 134.58, 85.07, 77.53, 68.10, 29.59, 29.59, 29.43,
29.32, 29.20, 28.88, 28.64, 27.57, 25.32, 19.37, 18.55 ppm.
EIMS (m/z, %): 262 (Mþ, 1), 247 (Mþ215, 1.5), 217 (6),
167 (7), 149 (14), 135 (24), 112 (100), 95 (78), 79 (45), 67
(89), 55 (57). HRMS (EI, m/z) calcd for C17H26O2 (M)þ:
262.1933. Found: 262.1922.
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4.1.10. (1)-(5S)-3(12-Dodecene)-5-methyl-2(5H)-fura-
none (3). Method A: To a solution of 41 mg (0.156 mmol)
of alkyne 2 in EtOAc (5 mL) were added Lindlar catalyst
(3 mg) and one drop of quinoline. After being stirred under
14. Sharpless, K. B.; Amber, W.; Bennani, Y. L.; Crispino, G. A.;