268
T.-Z. Liu, M. Isobe
LETTER
(5) Lewbart, M. L.; Schneider, J. J. J. Org. Chem. 1969, 34, 3505-
3512.
(4H, m, Ph). 13C NMR (100 MHz, CDCl3) d 14.0, 19.1, 21.2,
22.6, 26.6, 30.3, 31.5, 38.5, 40.3, 64.4, 7.9, 72.3, 77.2, 79.3,
80.4, 121.5, 127.8, 129.8, 133.1, 133.3, 135.6, 135.7, 141.2,
170.4, 199.7. MS (MALDI-TOF): calcd for C38H41Co2O11Si
m/z [M+H]+, 819.11; found, m/z 819.20.
(6) (a) Cha, J. K.; Christ, W. J.; Kishi, Y. Tetrahedron 1984, 40,
2247-2255. (b) Sharpless, K. B.; Amberg, W.; Bennani, Y. L.;
Crispino, G. A.; Hartung, J.; Jeong, K. S.; Kwong, H.-L.;
Morikawa, K.; Wang, Z.-M.; Xu, D.; Zhang, X.-L. J. Org.
Chem. 1992, 57, 2768-2771.
(7) Hosokawa, S.; Isobe, M. Tetrahedron Lett. 1998, 39, 2609-
2612.
(8) Sonogashira, K.; Tohda, Y.; Hagihara, N. Tetrahedron Lett.
1975, 4467-4470.
(11) (a) Nicholas, K. M.; Pettit, R. Tetrahedron Lett. 1971, 37,
3475-3478. (b) Cusack, N. J.; Reese, C. B.; Roozpeikar, B. J.
Chem. Soc., Chem. Commun. 1972, 1132-1133. (c) Cusack, N.
J.; Reese, C. B.; Risius, A. C.; Roozpeikar, B. Tetrahedron
1976, 32, 2157-2162.
(12) Cross peaks were observed between protons 7 and 4 as well as
7 and 10 in the NOESY experiments for compound 8b.
(13) Rasmussen, J. R. J. Org. Chem. 1980, 45, 2725-2727.
(14) Barton, D. H. R.; McCombie, S. W. J. Chem. Soc., Perkin
Trans. 1 1975, 1574-1585.
(9) Compound 4 was synthesized as follows:
(15) Data of the lactone 13: mp (°C):127-129. [a]D27 -59.2 (c 0.20,
CHCl3). 1H NMR (300 MHz, CDCl3) d 1.08 (3H, d, J = 7.0
Hz, CH3), 1.45-1.52 (1H, m, H-3a), 1.59-1.69 (4H, m,
H-2 x 2, H-6a, H-8a), 1.79-1.92 (2H, m, H-6b, H-7), 2.03-2.10
(3H, m, H-3b, H-8b, H-11a), 2.39 (1H, dt, J = 13.8, 7.8 Hz,
H-11b), 3.05 (1H, td, J = 10.0, 2.8 Hz, H-5), 3.15 (1H, td,
J = 10.0, 4.8 Hz, H-4), 3.23-3.31 (1H, m, H-1a), 3.64 (1H, td,
J = 9.5, 6.0 Hz, H-10), 3.83 (1H, br d, J = 11.0 Hz, H-1b), 3.95
(1H, dd, J = 8.5, 6.0 Hz, H-12), 4.35 (1H, ddd, J = 11.0, 9.5,
3.5 Hz, H-9), 4.66 (1H, d, J = 12.0 Hz, PhCH2O), 4.89 (1H, d,
J = 12.0 Hz, PhCH2O), 7.30-7.39 (5H, m, Ph). 13C NMR (75
MHz, CDCl3) d 25.8, 27.8, 32.4, 36.2, 45.2, 45.6, 67.5, 72.1,
72.3, 80.1, 81.9, 82.0, 85.3, 128.1, 128.5, 137.2, 169.8. IR
(KBr): nmax 1749, 1685, 1508, 1458, 1266, 1181, 1115, 947
cm-1. Anal. Calcd for C21H28O5: C, 69.98; H, 7.83. Found: C,
70.14; H, 8.02.
Reagents, conditions and yields: a) BH3∑SMe2, B(OMe)3,
THF, 0 °C, then MeOH workup. b) acetone, TsOH (cat), r.t.,
81% (2 steps). c) DMSO, (COCl)2, Et3N, CH2Cl2, -78-0 °C. d)
trimethylsilylacetylene, n-BuLi, THF, -78-0 °C, 53% (2
steps). e) DMSO, KOH powder, CH3I, 82%.
(10) Selected data of compound 7: [a]D26+26.0 (c 0.03, CHCl3). 1H
NMR (300 MHz, CDCl3) d 1.24-1.31 (1H, m, H-3a), 1.53-
1.56 (2H, m, H-2 x 3), 1.79 (1H, br d, J = 11.8, H-3b), 1.95
(1H, ddd, J = 14.2, 10.0, 5.2 Hz, H-11a), 2.06 (3H, s,
CH3CO), 2.39 (1H, ddd, J = 14.2, 10.0, 2.6 Hz, H-11b), 2.61
(1H, dd, J = 14.0, 2.0 Hz, H-6a), 2.72 (1H, dd, J = 14.0, 4.5
Hz, H-6b), 3.08 (1H, ddd, J = 11.0, 9.5, 4.8 Hz, H-4), 3.25-
3.33 (2H, m, H-1a, H-5), 3.78 (1H, dd, J = 12.0, 4.0 Hz, H-
13a), 3.83 (1H, dd, J = 12.0, 4.0 Hz, H-13b), 3.89 (1H, dt,
J = 11.8, 2.5 Hz, H-1b), 4.79 (1H, dd, J = 10.0, 3.0 Hz, H-10),
5.28 (1H, m, H-12), 5.42 (1H, d, J = 1.5 Hz, C=CH2), 5.54
(1H, d, J = 2.0 Hz, C=CH2), 7.35-7.43 (6H, m, Ph), 7.65-7.69
Article Identifier:
1437-2096,E;2000,0,02,0266,0268,ftx,en;Y20899ST.pdf
Synlett 2000, No. 2, 266–268 ISSN 0936-5214 © Thieme Stuttgart · New York