Absolute configuration of amphidinol 3, the first complete structure determination from amphidinol homologues: Application of a new configuration analysis based on carbon-hydrogen spin-coupling constants [8]

Journal of the American Chemical Society

Volumn 121, Issue 4, 1999, Pages 870-871

  Murata, Michio ^a   Matsuoka, Shigeru ^a   Matsumori, Nobuaki ^a   Paul, Gopal K ^a   Tachibana, Kazuo ^a  

^a UNIVERSITY OF TOKYO   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

AMPHIDINOL 3; NATURAL PRODUCT; UNCLASSIFIED DRUG;

BINDING KINETICS; DINOFLAGELLATE; DRUG ISOLATION; DRUG SYNTHESIS; FLAGELLATE; LETTER; STEREOCHEMISTRY; STRUCTURE ANALYSIS;

EID: 0033518615     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja983655x     Document Type: Letter

References (21)

1. (a) Satake, M.; Murata, M.; Yasumoto, T.; Fujita, T.; Naoki, H. J. Am. Chem. Soc. 1991, 113, 9859-9861.
2. (b) Paul, G. K.; Matsumori, N.; Murata, M.; Tachibana, K. Tetrahedron Lett. 1995, 36, 6279-6282.
3. The planar structure of 1: (c) Paul, G. K.; Matsumori, N.; Konoki, K.; Sasaki, M.; Murata, M.; Tachibana, K. In Harmful and Toxic Algal Blooms; Yasumoto, T., Oshima, Y., Fukuyo, Y., Eds.; UNESCO: Paris, 1996; pp 503-506.
4. Doi, Y.; Ishibashi, M.; Nakamichi, H.; Kosaka, T.; Ishikawa, T.; Kobayashi, J. J. Org. Chem. 1997, 62, 3820-3823.
5. (a) Matsumori, N.; Kaneno, D.; Murata, M.; Nakamura, H.; Tachibana, K. J. Org. Chem. in press.
6. Applications of this method have been published. (b) Matsumori, N.; Nonomura, T.; Sasaki, M.; Murata, M.; Tachibana, K.; Satake, M.; Yasumoto, T. Tetrahedron Lett. 1996, 37, 1269-1272.
7. Ohtani, I.; Kusumi, T.; Kashman, Y.; Kakisawa, H. J. Am. Chem. Soc. 1991, 113, 4092-4096.
8. Griesinger, C.; Sørensen, O. W.; Ernst, R. R. J. Am. Chem. Soc. 1985, 107, 6394-6396.
9. Kurz, M.; Schmieder, P.; Kessler, H. Angew. Chem., Int. Ed. Engl. 1991, 30, 1329-1331.
10. Zhu, G.; Live, D.; Bax, A. J. Am. Chem. Soc. 1994, 116, 8370-8371.
11. C,H on the dihedral orientation of oxygen functions has been investigated (e.g., Schwarcz, J. A.; Cyr, N.; Perlin, A. S. Can. J. Chem. 1975, 53, 1872-1875).
12. 3a Diastereomeric relations between C24 and C25, C33 and C34, C43 and C44, and C49 and C50 were established by key NOEs between H-23 and C25-OH, H-32 and H-38, C43-OH and H-45, and H-45 and H-51, respectively. See Supporting Information for details.
13. MTPA esters 2b (690 μg), 2c (520 μg), 3b (30 μg), 4b (400 μg), and 4c (150 μg) were obtained from 3.0 mg of 1. See Supporting Information.
14. As shown below, the stereochemistry at C6 and C14 can be determined to be 6R and 14R based on the distribution of Δδ (2b - 2c), in which positive values are observed in C15-C20, while negative ones are seen in C2-C5. The configuration of C10 could also be assigned since Δδ of C8 and C12 are zero. This can only be accounted for by the R configuration at C10, since the shielding effect at C8 (or C12) from a phenyl group of (S)-MTPA at C10 (or C14) should be equal to that from an (R)-MTPA at C6 (or C10). (Matrix Presented)
15. 2-70, +0.33/+0.42. These data show that C39 has an R configuration, since the clear separation of negative and positive values with respect to C39 shows that the Δδ values were predominately affected by the MTPA group on C39 rather than by other MTPA groups on relatively remote sites.
16. 3, 500 MHz) δ 3.98, 3.92, 3.82, 3.73, 1.53, 1.38, 1.05, 0.52. (R)-ester δ 3.97, 3.93, 3.83, 3.70, 1.52, 1.38, 1.05, 0.52.
17. A procedure that was previously reported for ciguatoxin was followed: Satake, M.; Morohashi, A.; Oguri, H.; Oishi, T.; Hirama, H.; Harada, N.; Yasumoto, T. J. Am. Chem. Soc. 1997, 119, 11325-11326.
18. Chiral resolution was performed on CHIRALPAK AD (ø 4.6 × 250 mm, DAICEL) eluted with hexane-1-propanol (25: 1). Authentic (S)-ester and the derivative from 1 (5b) were eluted at 16 min 50 sec and 16 min 59 sec, respectively, while (R)-ester appeared at 19 min 13 sec.
19. Schreiber, S. L.; Goulet, M. T. Tetrahedron Lett. 1987, 28, 6001-6004.
20. Lancelin, J.-M.; Beau J.-M. Tetrahedron Lett. 1989, 30, 4521-4524.
21. Rychnovsky, S. D.; Griesgraher, G.; Schlegel, R. J. Am. Chem. Soc. 1995, 117, 197-210.