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DOI: 10.1055/s-2001-15066
Fusicoccin Synthesis by Intramolecular [4+4] Photocycloaddition of 2-Pyridones: Stereocontrol of the Cycloaddition and Elaboration of the Pentacyclic Product[*]
Publikationsverlauf
received 05. März 2001
revised 29. März 2001
Publikationsdatum:
24. September 2004 (online)
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Abstract
Intramolecular photocycloaddition of a three-carbon tethered pyrindinone–pyridone system yields the 5-8-5 ring system of the fusicoccin/ophiobolin/ceroplastol families. The stereoselectivity of the cycloaddition was found to be dependent on nitrogen substitution; N-methylation led to exclusively trans products while an absence of nitrogen substitution resulted in solvent-dependent stereoselectivity. Solvent and concentration effects for this cycloaddition were consistent with a hydrogen-bonded dimer that enforces a pro-cis conformation in nonpolar solvents and at higher concentrations. The cis-isomer, a fusicoccin synthesis intermediate, underwent a Cope rearrangement at ambient temperature but could be trapped efficiently as the mono epoxide, yielding a product with six new stereogenic centers. A four-step transformation of an amide carbonyl to a methyl group was achieved using a carbamoyl group to activate the amide for cleavage.
Key words
fusicoccin - higher-order cycloadditions - photochemistry - stereoselectivity - solvent effects* Dedicated to Howard Zimmerman on the occasion of his 75th birthday
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References
-
1 Current address: Albany Molecular Research, Inc., Albany, NY 12203, USA.
-
2 Current address: An-Najah National University, Nablus, Palestine.
-
3 (a) Kato, N.; Kataoka, H.; Ohbuchi, S.; Tanaka, S.; Takeshita, H. J. Chem. Soc., Chem. Commun. 1988, 354. (b) Rowley, M.; Tsukamoto, M.; Kishi, Y. J. Am. Chem. Soc. 1989, 111, 2735. (c) Boeckman, R. K. Jr.; Arvanitis, A.; Voss, M. E. J. Am. Chem. Soc. 1989, 111, 2737. (d) Kato, N.; Takeshita, H.; Kataoka, H.; Ohbuchi, S.; Tanaka, S. J. Chem. Soc., Perkin Trans. 1 1989, 165. (e) Paquette, L. A.; Wang, T.-Z.; Vo, N. H. J. Am. Chem. Soc. 1993, 115, 1676. (f) Jamison, T. F.; Shambayati, S.; Crowe, W. E.; Schreiber, S. L. J. Am. Chem. Soc. 1994, 116, 5505. (g) Okamoto, H.; Arita, H.; Kato, N.; Takeshita, H. Chem. Lett. 1994, 2335. (h) Paquette, L. A.; Sun, L.-Q.; Friedrich, D.; Savage, P. B. Tetrahedron Lett. 1997, 38, 195. (i) Kato, N.; Zhang, C.-S.; Matsui, T.; Iwabuchi, H.; Mori, A.; Ballio, A.; Sassa, T. J. Chem. Soc., Perkin Trans. 1 1998, 2473.
-
4 (a) A portion of this work was the subject of a communication: Sieburth, S. McN.; McGee, K. F. Jr.; Al-Tel, T. H. Tetrahedron Lett. 1999, 40, 4007. (b) See also Refs 17 and 18.
-
5 Sieburth, S. McN. The Inter- and Intramolecular [4 + 4] Photocycloaddition of 2-Pyridones and Its Application to Natural Product Synthesis, In Advances in Cycloaddition, Vol. 5; Harmata, M., Ed.; JAI: Greenwich CT, 1999, 85– 118.
-
6 Nakamura, Y.; Kato, T.; Morita, Y. Tetrahedron Lett. 1981, 22, 1025.
-
7 See Sieburth, S. McN.; Lin, C.-H. J. Org. Chem. 1994, 59, 3597; and references cited therein.
-
8 Sieburth, S. McN.; Hiel, G.; Lin, C.-H.; Kuan, D. P. J. Org. Chem. 1994, 59, 80.
-
9 Paine, J. B. III J. Heterocycl. Chem. 1987, 24, 351.
-
10 Hopkins, G. C.; Jonak, J. P.; Minnemeyer, H. J.; Tieckelmann, H. J. Org. Chem. 1967, 32, 4040.
-
11 Chung, N. M.; Tieckelmann, H. J. Org. Chem. 1970, 35, 2517.
-
12 Compound 21 crystallizes in the monoclinic space group P21/n with a=10.541(3) Å, b=16.593(2) Å, c=26.791(6) Å, b=90.36(1)°, V=4686(2) Å3, and Z=4. Final least squares refinement using 1622 unique reflections with I > 3s(I) gave R1 (wR2)=0.060 (0.055)
-
13 Taylor, E. C.; Kan, R. O. J. Am. Chem. Soc. 1963, 85, 776.
-
14 Paquette, L. A.; Slomp, G. J. Am. Chem. Soc. 1963, 85, 765.
-
15 Meyers, A. I.; Singh, P. J. Org. Chem. 1970, 35, 3022.
-
16 (a) Ducharme, Y.; Wuest, J. D. J. Org. Chem. 1988, 53, 5787. (b) Gallant, M.; Phan Viet, M. T.; Wuest, J. D. J. Am. Chem. Soc. 1991, 113, 721. (c) Simard, M.; Su, D.; Wuest, J. D. J. Am. Chem. Soc. 1991, 113, 4696. (d) Persico, F.; Wuest, J. D. J. Org. Chem. 1993, 58, 95. (e) Gallant, M.; Phan Viet, M. T.; Wuest, J. D. J. Org. Chem. 1991, 56, 2284. (f) Boucher, E.; Simard, M.; Wuest, J. D. J. Org. Chem. 1995, 60, 1408.
-
17 Sieburth, S. McN.; McGee, K. F. Jr.; Al-Tel, T. H. J. Am. Chem. Soc. 1998, 120, 587.
-
18 Sieburth, S. McN.; McGee, K. F. Jr. Org. Lett. 1999, 1, 1775.
-
19 Reichardt, C. Solvents and Solvent Effects in Organic Chemistry, 2nd ed.; VCH: New York, 1988.
-
20 Vogel, E. Liebigs Ann. Chem. 1958, 615, 1.
-
21 Carpenter, B. K. Tetrahedron 1978, 34, 1877.
-
22 Delbecq, F.; Anh, N. T. New J. Chem. 1983, 7, 505.
-
23 Dollinger, M.; Henning, W.; Kirmse, W. Chem. Ber. 1982, 115, 2309.
-
24 Sieburth, S. McN.; Chen, J.; Ravindran, K.; Chen, J.-l. J. Am. Chem. Soc. 1996, 118, 10803.
-
25 Murray, R. W. Chem. Rev. 1989, 89, 1187.
-
26 Adam, W.; Curci, R.; Edwards, J. O. Acc. Chem. Res. 1989, 22, 205.
-
27 Curci, R.; Dinoi, A.; Rubino, M. F. Pure Appl. Chem. 1995, 67, 811.
-
28 Flynn, D. L.; Zelle, R. E.; Grieco, P. A. J. Org. Chem. 1983, 48, 2424.
-
29 Sieburth, S. McN.; Rucando, D.; Lin, C.-H. J. Org. Chem. 1999, 64, 954.
-
30 For a related example that does not involve ring opening when a Boc-activated lactam of a pyridone photodimer is reduced see: Spivey, A. C.; Andrews, B. I.; Brown, A. D.; Frampton, C. S. Chem. Commun. 1999, 2523.
-
31 Compound 30 crystallizes from MeCN in the monoclinic space group P21/c with a=15.126(4) Å, b=12.900(3) Å, c=15.592(4) Å, β=111.70(2)°, V=2826.9(5) Å3, and Z=4. Final least squares refinement using 2229 unique reflections with I > 3s(I) gave R1 (wR2)=0.069 (0.088)
-
32 Katagiri, N.; Muto, M.; Nomura, M.; Higashikawa, T.; Kaneko, C. Chem. Pharm. Bull. 1991, 39, 1112.
-
33 Fujimoto, Y.; Tatsuno, T. Tetrahedron Lett. 1976, 3325.
-
34 Matsumoto, T.; Terao, H.; Wada, M.; Imai, S. Bull. Chem. Soc. Jpn. 1991, 64, 2762.
-
35 (a) Paquette, L. A. US Patent 3 321 482, 1967. (b) Chem. Abstr. 1968, 68, 49577. (c) Paquette, L. A. US Patent 3 318 899, 1967. (d) Chem. Abstr. 1968, 68, 49579. (e) Paquette, L. A. US Patent 3 432 507, 1969. (f) Chem. Abstr. 1969, 70, 96834. (g) Paquette, L. A. US Patent 3 466 292, 1969. (h) Chem. Abstr. 1970, 72, 12781. (i) Paquette, L. A. US Patent 3 562 252, 1971. (j) Chem. Abstr. 1971, 75, 20454.