C. K. Malik et al. / Tetrahedron Letters 50 (2009) 3063–3066
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Soc. 1997, 119, 11353.
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Danishefsky, S. J. J. Am. Chem. Soc. 1999, 121, 6563.
7. Construction of a B/C ring analogue through RCM of an analogous divinyl
system has been reported recently. See Ref. 4o.
8. (a) Stragies, R.; Blechert, S. Synlett 1998, 169; (b) Weatherhead, G. S.; Ford, J. G.;
Alexanian, E. J.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc. 2000, 122, 1828;
(c) Hagiwara, H.; Katsumi, T.; Endou, S.; Hoshi, T.; Suzuki, T. Tetrahedron 2002,
58, 6651; (d) Wrobleski, A.; Sahasrabudhe, K.; Aube, J. J. Am. Chem. Soc. 2004,
126, 5475; (e) Weatherhead, G. S.; Cortez, G. A.; Schrock, R. R.; Hoveyda, A. H.
Proc. Natl. Acad. Sci. U.S.A. 2004, 101, 5805; (f) Holtsclaw, J.; Koreeda, M. Org.
Lett. 2004, 6, 3719; (g) Hart, A. C.; Phillips, A. J. J. Am. Chem. Soc. 2006, 128,
1094; (h) Maechling, S.; Norman, S. E.; Mckendrick, J. E.; Basra, S.; Koppner, K.;
Blechert, S. Tetrahedron Lett. 2006, 47, 189; (i) Malik, C. K.; Ghosh, S. Org. Lett.
2007, 9, 2537; (k) Maity, S.; Ghosh, S. Tetrahedron Lett. 2008, 49, 1133; (l)
Mondal, S.; Malik, C. K.; Ghosh, S. Tetrahedron Lett. 2008, 49, 5649.
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Takemoto, Y. J. Org. Chem. 2001, 66, 81; (b) Takahashi, T.; Watanabe, H.;
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Figure 1. ORTEP diagram of compound 20.
age of the resulting vicinal diol afforded the aldehyde 17. Addition
of vinyl magnesium bromide to the aldehyde 17 and subsequent
oxidation of the carbinol afforded the required enone 18. Diels–Al-
der reaction of the enone 18 with cyclopentadiene in the presence
of anhydrous ZnCl2 as catalyst was found to be highly diastereose-
lective producing exclusively the adduct 19 in 92% isolated yield.
The structure of the adduct 19 was established by determination
of X-ray crystal structure (Fig. 1)11 of the hydroxy compound 20
obtained through removal of PMB protecting group. The hydroxy
compound 20 was then transformed to the ester 21 on reaction
with acryloyl chloride. Unlike metathesis of 13, metathesis of the
compound 21 with the catalyst 14 under identical condition gave
quantitatively the ring-opened product 22. However, the ring-
opened product 22 could be cyclized using the catalyst 23 to pro-
duce the fused bicycle 24 containing nine-membered lactone in
65% yield (based on recovered 22). The structure of the compound
24 was established through spectral data. The tricycle 24 contains
all necessary functional groups for transformation to the core
structure of 1–3.
10. Czernecki, S.; Gorson, G. Tetrahedron Lett. 1978, 4113.
11. Crystal data for compound 20:
A
plate-shaped colourless crystal
(0.3 ꢁ 0.24 ꢁ 0.08) was analyzed. C15H20O5, Mr = 280.31, monoclinic, space
group P2(1) (no. 4) a = 10.337(4), b = 5.798(2), c = 13.054(5) Å, b = 113.295(5),
V = 718.6(5) Å3, T = 100 K, Z = 2.
q
calcd = 1.295 g cmꢀ3. F (0 0 0) = 300, k (Mo
K
a
) = 0.71073 Å,
observed (I > 2
(I > 2 (I)), R1 = 0.0347; wR2 = 0.0780 (all data) with GOF = 1.045. X-ray single
crystal data were collected using Mo K (k = 0.7107 Å) radiation on a SMART
l
Mo
Ka
/mmꢀ1 = 0.097, 3193 reflections measured, 761
r
(I)) 187 parameters; Rint = 0.0345, R1 = 0.0305; wR2 = 0.0753
r
a
APEX diffractometer equipped with CCD area detector. The structure was
solved by direct method and was refined in a routine manner. Crystallographic
data for compound 20 have been deposited with the Cambridge
Crystallographic Data Centre as supplementary publication No. CCDC
708798. Copies of the data can be obtained, free of charge, on application to
CCDC, 12 Union Road, Cambridge CB2 1EZ, UK. Fax: +44 1223-336033. E-mail:
In conclusion we have developed a protocol for convenient ac-
cess to nine-membered cyclic ether and nine-membered lactone
fused to a functionalized cyclopentane ring. The fused bicycle with
the nine-membered lactone is a potential intermediate to the syn-
thesis of eleutherobin and sarcodictyns.
12. All new compounds were characterized on the basis of IR, 1H, 13C NMR and
HRMS data. Spectral data for selected compounds: Compound 13: IR
m
max = 1708 cmꢀ1 , ½a D26
ꢂ
ꢀ 112 (c 0.28, CHCl3); 1H NMR (300 MHz, CDCl3) d
1.28 (1H, m), 1.31 (3H, s), 1.37–1.42 (2H, m), 1.45 (3H, s), 1.74–1.82 (1H, ddd,
J = 3.6, 8.9, 11.9 Hz), 2.85 (1H, br s), 3.23 (1H, br s), 3.33–3.39 (1H, m), 3.94 (1H,
dd, J = 5.8, 12.8 Hz), 4.03 (1H, dd, J = 5.3, 12.7 Hz), 4.19 (1H, d, J = 3.6 Hz), 4.54
(1H, d, J = 3.8 Hz), 4.65 (1H, d, J = 3.6 Hz), 5.16–5.27 (2H, m), 5.74–5.79 (1H, m),
5.83 (1H, dd, J = 2.2, 5.4 Hz), 6.05 (1H, d, J = 3.6 Hz), 6.12 (1H, dd, J = 3.1,
5.3 Hz); 13C NMR (75 MHz, CDCl3) d 26.4 (CH3), 26.9 (CH3), 28.8 (CH2), 42.8
(CH), 46.2 (CH), 48.7 (CH), 50.1 (CH2), 71.4 (CH2), 82.0 (CH), 83.1 (CH), 85.6
(CH), 105.7 (CH), 112.2 (C), 118.2 (CH2@), 132.3 (CH@), 133.7 (CH@), 137.1
(CH@), 208.1 (CO); HRMS (ESI) calcd for C18H24O5Na (M+Na)+, 343.1521; found
Acknowledgements
Financial support from the Department of Science and Technol-
ogy, Government of India through Ramanna Fellowship to S.G. is
gratefully acknowledged. C.K.M. and M.F.H. thank CSIR, New Delhi
for Research Fellowships. We thank DST for funds for National Sin-
gle Crystal Diffractometer facility at the Department of Inorganic
Chemistry.
343.1525. Compound 15: IR
m
max = 1707 cmꢀ1; ½a D26
ꢂ
ꢀ 77:6 (c 2.4, CHCl3); 1H
NMR (500 MHz, CDCl3) d 1.33 (3H, s), 1.36–1.40 (1H, m), 1.48 (3H, s), 1.82 (2H,
t, J = 10.0 Hz), 2.19 (1H, td, J = 6.4, 7.6 Hz), 2.56 (1H, sextet, J = 8.6 Hz), 3.42 (1H,
quintet, J = 8.7 Hz), 3.82 (1H, dd, J = 10.6, 15.0 Hz), 4.00 (1H, q, J = 9.6 Hz), 4.04
(1H, d, J = 1.7 Hz), 4.33 (1H, d, J = 2.3 Hz), 4.40 (1H, d, J = 15.0 Hz), 4.53 (1H, d,
J = 3.1 Hz), 4.96 (1H, d, J = 10.3 Hz), 5.06 (1H, d, J = 17.1 Hz), 5.51 (1H, dt, J = 4.0,
10.5 Hz), 5.57 (1H, dt, J = 2, 10.5 Hz), 5.85 (1H, tdd, J = 7.2, 10.0, 18.0 Hz), 6.09
(1H, d, J = 3.2 Hz); 13C NMR d 26.5 (CH3), 26.9 (CH3), 35.8 (CH2), 40.3 (CH), 41.2
(CH2), 44.4 (CH), 51.1 (CH), 68.6 (CH2), 84.3 (CH), 85.5 (CH), 86.3 (CH), 105.9
(CH), 112.8 (C), 113.7 (CH2@), 125.2 (CH@), 141.6 (CH@), 141.7 (CH@), 211.8
(CO); HRMS (ESI) calcd for C18H24O5Na (M+Na)+, 343.1521; found 343.1524.
References and notes
1. Lindel, T.; Jensen, P. R.; Fenical, W.; Long, B. H.; Casazza, A. M.; Carboni, J.;
Fairchild, C. R. J. Am. Chem. Soc. 1997, 119, 8744.
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D’Ambrosio, M.; Guerriero, A.; Pietra, R. Helv. Chim. Acta 1988, 71, 964.
3. Schiff, P. B.; Fant, J.; Horwitz, S. B. Nature 1979, 277, 665.
4. (a) Lindel, T. Angew. Chem., Int. Ed. 1998, 37, 774; (b) Ceccarelli, S.; Piarulli, U.;
Gennari, C. Tetrahedron Lett. 1999, 40, 153; (c) Baron, A.; Caprio, V.; Mann, J.
Tetrahedron Lett. 1999, 40, 9321; (d) Tsypysheva, I. P.; Kunakova, A. M.; Valeev,
F. A.; Tolstikov, G. A. Chem. Nat. Compd. 2001, 37, 490; (e) By, K.; Kelly, P. A.;
Kurth, M. J.; Olmstead, M. M.; Nantz, M. H. Tetrahedron 2001, 57, 1183; (f)
Ceccarelli, S.; Piarulli, U.; Gennari, C. Tetrahedron 2001, 57, 8531; (g) Ceccarelli,
Compound 19: IR
m
max = 1705 cmꢀ1
;
½
a 2D5
ꢂ
ꢀ 88:4 (c 3.0, CHCl3); 1H NMR
(300 MHz, CDCl3) d 1.13–1.18 (2H, m), 1.25 (3H, s), 1.27–1.37 (1H, m), 1.39 (3H,
s), 1.69 (1H, ddd, J = 3.3, 8.7, 11.7 Hz), 2.77 (1H, br s), 3.10 (1H, br s), 3.12–3.16
(1H, m), 3.72 (3H, s) 4.20 (1H, d, J = 3.6 Hz), 4.34 (1H, d, J = 11.6 Hz), 4.47 (1H, d,
J = 11.6 Hz), 4.51 (1H, d, J = 3.6 Hz), 4.62 (1H, d, J = 3.6 Hz), 5.70 (1H, dd, J = 2.4,
5.4 Hz) 6.00 (1H, d, J = 3.6 Hz), 6.04 (1H, dd, J = 3.1, 5.2 Hz), 6.80 (2H, d,
J = 8.5 Hz), 7.12 (2H, d, J = 8.5 Hz); 13C NMR (75 MHz, CDCl3) d 26.4 (CH3), 27.0
(CH3), 28.6 (CH2), 42.6 (CH), 46.2 (CH), 48.8 (CH), 50.0 (CH2), 55.3 (OMe), 72.0
(CH2), 81.8 (CH), 82.8 (CH), 85.4 (CH), 105.6 (CH), 112.1 (C), 113.9 (2 CH), 129.O
(C), 129.7 (2 CH), 132.2 (CH@), 137.1 (CH@), 159.6 (C), 207.5 (CO); HRMS (ESI)