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K.; Ishida, N., Eds.; Springer: Tokyo, 1997. (b) Xi, Z.;
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2.3 Hz, CH2N), 3.83 (s, 3H), 4.19 (d, 1H, J¼11.7 Hz,
CH2OMPM), 4.20 (d, 1H, J¼11.2 Hz), 4.27 (d, 1H,
J¼11.2 Hz), 4.62 (d, 1H, J¼11.7 Hz, CH2OMPM), 4.88
(dd, 1H, J¼14.1, 10.8 Hz, CH2N), 5.00 (dd, 1H, J¼10.8,
2.3 Hz, NH), 5.22 (t, 1H, J¼7.8 Hz), 5.35 (s, 1H, H-8), 5.61
(dd, 1H, J¼10.7, 4.8 Hz), 5.87 (dd, 1H, J¼3.5, 1.4 Hz,
H-12), 6.34 (d, 1H, J¼8.3 Hz, H-40), 6.86 (d, 1H, J¼8.3 Hz,
H-50), 6.92 (d, 2H, J¼8.8 Hz), 7.04 (s, 1H, H-3), 7.18 (d,
2H, J¼8.8 Hz), 7.30 (s, 1H, H-6). 13C NMR (125 MHz,
CDCl3) d 25.17, 25.03, 24.77, 24.39, 23.21, 23.06,
17.77, 18.13, 18.42, 25.61, 25.66, 26.00, 38.47 (C14), 43.55,
48.98, 54.88, 55.24, 67.54, 70.39 (C5), 70.57, 70.79, 83.76
(C8), 92.45 (C9), 110.19, 113.88, 120.24, 121.91 (C3),
122.10, 128.97, 129.21, 129.72, 131.44 (C6), 133.47,
135.81 (C4), 136.12 (C2), 138.96 (C13), 142.33, 144.30
(C7), 150.06 (C1), 153.95, 159.33, 168.34. HMBC
correlations: H3–C1, H3–C7, H3–C5, H3–C13; H5–C3,
H5–C4, H5–C13; H6–C2, H6–C4, H6–C8, H6–C14.
MALDI-TOFMS (positive-ion) calcd for C50H74ClNO8Si3-
Na: (MþNa)þ 958.4308; found: 958.4375, calcd for
C50H74ClNO8Si3K: (MþK)þ 974.4048; found 974.4182.
6. For recent synthetic studies on nine-membered endiyne
antibiotics, see: (a) Myers, A. G.; Hogan, P. C.; Hurd, A. R.;
Goldberg, S. D. Angew. Chem. Int. Ed. Engl. 2002, 41, 1062.
(b) Myers, A. G.; Glatthar, R.; Hammond, M.; Harrington,
P. M.; Kuo, E. Y.; Liang, J.; Schaus, S. E.; Wu, Y.; Xiang,
J.-N. J. Am. Chem. Soc. 2002, 124, 5380. (c) Kobayashi, S.;
Ashizawa, S.; Takahashi, Y.; Sugiura, Y.; Nagaoka, M.; Lear,
M. J.; Hirama, M. J. Am. Chem. Soc. 2001, 123, 11294.
(d) Kobayashi, S.; Reddy, R. S.; Sugiura, Y.; Sasaki, D.;
Miyagawa, N.; Hirama, M. J. Am. Chem. Soc. 2001, 123,
2887. (e) Myers, A. G.; Liang, J.; Hammond, M.; Harrington,
P. M.; Wu, Y.; Kuo, E. Y. J. Am. Chem. Soc. 1998, 120, 5319.
(f) Myers, A. G.; Goldberg, S. D. Angew. Chem. Int. Ed. Engl.
2000, 39, 2732. (g) Magnus, P.; Carter, R.; Davies, M.; Elliott,
J.; Pitterna, T. Tetrahedron 1996, 52, 6283. (h) Caddick, S.;
Delisser, V. M.; Doyle, V. E.; Khan, S.; Avent, A. G.; Vile, S.
Tetrahedron 1999, 55, 2737. (i) Tanaka, H.; Yamada, H.;
Matsuda, A.; Takahashi, T. Synlett 1997, 381, and references
cited therein.
Acknowledgements
This work was supported by CREST, Japan Science and
Technology Corporation (JST). We thank Dr. Chizuko
Kabuto for her assistance in X-ray crystallographic analysis,
and Mr. Kazuo Sasaki for his detailed NMR spectroscopic
analysis. A fellowship to N. K. from the Japanese Society
for the Promotion of Science (JSPS) for Young Japanese
Scientists and a postdoctoral fellowship to S. K. from JSPS
are gratefully acknowledged. We are grateful to ZEON
CORPORATION for cyclopentenone.
7. Yoshimura, F.; Kawata, S.; Hirama, M. Tetrahedron Lett.
1999, 40, 8281.
References and notes
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