Synthesis of the B,C,D,E,F-ring fragment of pinnatoxins

Synlett

Volumn , Issue 5, 1999, Pages 541-544

  Sugimoto, Tetsuya ^a   Ishihara, Jun ^a   Murai, Akio ^a  

^a HOKKAIDO UNIVERSITY   (Japan)

Author keywords

Dispiroacetal; Pinnatoxin; Trioxadispiro 5.1.5.2 pentadecane dioxabicyclo 3.2.1 octane

Indexed keywords

MARINE TOXIN; PINNATOXIN; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL MODIFICATION; CHEMICAL REACTION; CHEMICAL STRUCTURE; EPOXIDATION; ISOMERISM; OXIDATION; REACTION ANALYSIS; STEREOCHEMISTRY; SYNTHESIS;

EID: 0032939222     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-1999-2689     Document Type: Article

References (18)

1. (a) Uemura, D.; Chou, T.; Haino, T.; Nagatsu, A; Fukuzawa, S.; Zeng, S. Z.; Chen, H. S. J. Am. Chem. Soc. 1995, 117, 1155.
2. (b) Chou, T.; Kamo, O.; Uemura, D. Tetrahedron Lett. 1996, 37, 4023.
3. (c) Chou, T.; Haino, T.; Kuramoto, M.; Uemura, D. Tetrahedron Lett. 1996, 37, 4027;
4. (d) The absolute configuration of natural pinnatoxin A was determined synthetically as enantiomer of 1: McCauley, J. A.; Nagasawa, K.; Lander, P. A.; Mischke, S. G.; Semones, M. A.; Kishi, Y. J. Am. Chem. Soc. 1998, 120, 7647.
5. Synthetic studies on pinnatoxins: (a) Noda, T; Ishiwata, A.; Uemura, S.; Sakamoto, S.; Hirama, M. Synlett 1998, 298.
6. (b) Suthers, B. D.; Jacobs, M. F.; Kiching, W. Tetrahedron Lett. 1998, 39, 2621. Total synthesis of ent-pinnatoxin A (1): ref. 1d.
7. (a) Sugimoto, T.; Ishihara, J.; Murai, A. Tetrahedron Lett. 1997, 38, 7379.
8. (b) Ishihara, J.; Sugimoto, T.; Murai, A. Synlett 1998, 603.
9. 5 as follows: (figure presented)
10. Frick, J. A.; Klassen, J. B.; Bathe, A.; Abramson, J. M.; Rapoport, H. Synthesis 1992, 621.
11. Katsuki, T.; Lee, A. W. N.; Ma, P.; Martin, V. S.; Masamune, S.; Sharpless, K. B.; Tuddenham, D.; Walker, F. J. J. Org. Chem. 1982, 47, 1373.
12. (a) Isobe, M.; Kitamura, M.; Mio, S.; Goto, T. Tetrahedron Lett. 1982, 23, 221.
13. (b) Kitamura, M.; Isobe, M.; Ichikawa, Y.; Goto, T. J. Org. Chem. 1984, 49, 3517.
14. Maruyama, K.; Ueda, M.; Sasaki, S.; Iwata, Y.; Miyazawa, M.; Miyashita, M. Tetrahedron Lett. 1998, 39, 4517.
15. The relative energy differences among the model compounds are shown below: The calculation was performed by Cache Mechanics 3.6. (figure presented)
16. Since the solubility of 22 in MeCN was very low, THF was required as a co-solvent for larger scale reaction.
17. 3), δ 0.02 (3H, s), 0.04 (3H, s), 0.08 (6H, s), 0.82 (3H, d, J = 6.6 Hz, H36), 0.88 (9H, s), 0.90 (9H, s), 1.19 (1H, dq, J = 3.0, 12.7 Hz, H22ax), 1.28 (3H, s, H37), 1.41 (1H, brt, 7 = 13.5 Hz, H26ax), 1.42 (1H, m, H13ax), 1.50 (1H, dd, J = 5.8, 13.5 Hz, H26eq), 1.55 (1H, m, H20a), 1.56 (1H, m, H17a), 1.56 (1H, m, H21ax), 1.57 (1H, m, H13eq), 1.57 (1H, m, H14eq), 1.64 (1 H, m, H20b), 1.68 (2H, m, H11), 1.74 (1H, dd, 7 = 10.8, 14.0 Hz, H24a), 1.87 (1H, m, H18a), 1.88 (1H, m, H21eq), 1.95 (1H, m, H18b), 1.96 (1H, m, H22eq), 2.19 (1H, m, H27), 2.20 (1H, dd, J = 3.0, 14.0 Hz, H24b), 2.21 (1H, dt, 7 = 4.2, 13.2 Hz, H14ax), 2.28 (1H, dt, J = 9.3, 11.6 Hz, H17b), 3.47 (1H, m, H28), 3.49 (2H, t, J = 6.3 Hz, H10), 3.61 (1H, dd, J = 7.3, 10.0 Hz, H31a), 3.76 (1H, dd, 7 = 6.4, 10.0 Hz, H31b), 3.80 (3H, s, MPM), 3.95 (1H, m, H12), 4.12 (1H, m, H30), 4.13 (1H, m, H23), 4.21 (1H, dd, J = 2.0, 4.4 Hz, H29), 4.36 (1H, d, J = 11.5 Hz, MPM), 4.41 (1H, d, J = 11.5 Hz, MPM), 4.49 (1H, d, J = 12.4 Hz, Bn), 4.63 (1H, d, J = 12.4 Hz, Bn), 6.86 (2H, d, J = 8.8 Hz, MPM), 7.24 (2H, d, J = 8.8 Hz, MPM), 7.29-7.37 (5H, m, Bn).
18. 6), δ 0.05 (3H, s), 0.06 (3H, s), 0.10 (3H, s), 0.16 (3H, s), 0.97 (3H, d, J = 6.9 Hz, H36), 0.99 (9H, s), 1.00 (9H, s), 1.314 (3H, s, H37), 1.33-1.36 (1H, m), 1.38-1.42 (1H, m), 1.47-1.52 (1H, m), 1.61-1.93 (10H, m), 2.06 (1H, dt, J = 7.8, 13.8 Hz, H26ax), 2.10-2.20 (3H, m, H27, H11), 2.16 (1H, dd, J = 6.6, 14.5 Hz, H24a), 2.25-2.33 (2H, m), 2.44 (1H, dd, J = 5.0, 14.5 Hz, H24b), 3.32 (3H, s, MPM), 3.54 (1H, dd, J = 7.8, 9.4 Hz, H31a), 3.59 (1H, dd, J = 1.8, 4.0 Hz, H28), 3.69 (1H, dd, J = 5.5, 9.4 Hz, H31b), 3.76 (1H, m, H30), 3.97 (1H, m, H23), 4.19 (1H, d, J = 12.0Hz),4.32 (1H, d, J = 12.0 Hz), 4.32-4.42 (4H, m, H10, H12, H29), 4.47 (1H, d, J = 11.9 Hz), 4.53 (1H, d, J = 11.9 Hz), 6.85 (2H, d, J = 8.8 Hz, MPM), 7.10 (2H, m, Bn), 7.18-7.22 (3H, m, Bn), 7.37 (2H, d, J = 8.8 Hz, MPM).