Notes and references
‡ While this manuscript was submitted, Kozmin and co-workers reported
simultaneously a communication concerning the structure of a bistramide
A–actin complex.15
§ Experimental procedure for 5: bistramide Dda 4 (270.8 mg; 0.342 mmol)
and imidazole (76 mg; 3.26 equiv.) were dissolved under argon in DMF
(5 mL) and then TBDMSCl (177 mg; 3.43 equiv.) was added in one portion.
The mixture was stirred for16 h at room temperature before hydrolysis by
water (30 mL), and diluted with diethyl ether (50 mL). Vigorous stirring
was continued for 1.5 h and then the aqueous layer was extracted with
diethyl ether (2 × 15 mL). The combined organic layers were washed with
water (6 × 50 mL), brine (15 mL), dried (MgSO4), filtered and concentrated
under reduced pressure to obtain a crude product. The residue was purified
by column chromatography on silica gel (AcOEt–CH2Cl2 1 : 1) to afford
5 (231 mg; 74.6%) as a white solid. In order to have some crystals of
this compound for X-ray analysis, we recrystallized it in hot pentane.
◦
Mp = 127–128 C (pentane). [a]2D0 +84 (c 1.19 in CH2Cl2). Elemental
analysis for C50H88N2O10Si (905.327): calc. C, 66.33; H, 9.80; N, 3.09.
Found: C, 66.20; H, 9.92; N, 2.85%. H and 13C NMR data can be seen
in the ESI.
1
Scheme 3
¶ Crystal data for 5. C50H88N2O10Si, M = 905.31, monoclin◦ic, a =
˚
14.371(2), b = 9.5023(10), c = 21.501(3) A, b = 103.55(5) , V =
3
−1
˚
2854.4(6) A , T = 173 K, space group P1211, Z = 2, l = 0.091 mm
,
R = 0.0812, wR2 = 0.2129, 11 544 reflections measured, 3551 unique
(Rint = 0.07), the final R was 0.0812. CCDC reference number 255731.
For crystallographic data in CIF or other electronic format see DOI:
10.1039/b603767d.
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Fig. 1 ORTEP drawing of compound 5 (with 50% probability ellipsoids).
stereogenic centers. Furthermore, comparison of the structure
of the elucidated bistramides A, C and D underlines that the
observed biological activity is probably due to the fragment C1–
C11. Indeed, the C-4 hydroxy group present in bistramides D and
K (without the pyran moiety) is replaced by a carbonyl function
in bistramides A, C and B, which have been shown to be more
toxic. Also, in spite of the presence of a carbonyl function at C-39
for bistramide C – all other bistramides include a hydroxy group
at this position – we can therefore imagine that this position has
no effect on the biological activity.
In summary, we have determined the absolute configuration of
a chemical derivative of bistramide D by radiocrystallographic
analysis starting from the natural material. We assume that
the same absolute configuration can be extended to the related
bistramides K and B.
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Acknowledgements
15 S. A. Rizvi, V. Tereshko, A. A. Kossiakoff and S. A. Kozmin, J. Am.
Chem. Soc., 2006, 128, 3882–3883.
We are grateful to Professor H. D. Flack for helpful discussions.
1862 | Org. Biomol. Chem., 2006, 4, 1860–1862
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