Modular Approach toward the Construction of the Core Motifs of Annonaceous Acetogenins and Variants Thereof

Journal of Organic Chemistry

Volumn 63, Issue 5, 1998, Pages 1368-1369

  Zanardi, Franca ^a   Battistini, Lucia ^b   Rassu, Gloria ^b   Pinna, Luigi ^b   Mor, Marco ^b   Culeddu, Nicola ^b   Casiraghi, Giovanni ^b  

^a UNIVERSITY OF PARMA   (Italy)

^b NONE

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001671724     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo972031r     Document Type: Article

References (23)

1. Zeng, L.; Ye, Q.; Oberlies, N. H.; Shi, G.; Gu, Z.-M.; He, K.; McLaughlin, J. L. Nat. Prod. Rep. 1996, 13, 275. Cavé, A.; Figadère, B.; Laurens, A.; Cortes, D. In Progress in the Chemistry of Organic Natural Products; Hertz, W., Eds.; Springer-Verlag: Wien, New York, 1997; Vol. 70, p 81.
2. Zeng, L.; Ye, Q.; Oberlies, N. H.; Shi, G.; Gu, Z.-M.; He, K.; McLaughlin, J. L. Nat. Prod. Rep. 1996, 13, 275. Cavé, A.; Figadère, B.; Laurens, A.; Cortes, D. In Progress in the Chemistry of Organic Natural Products; Hertz, W., Eds.; Springer-Verlag: Wien, New York, 1997; Vol. 70, p 81.
3. Westley, J. W. Polyether Antibiotics: Naturally Occurring Acid Ionophores; Marcel Dekker: New York, 1983; Vols. 1 and 2.
4. Total syntheses: Hoye, T. R.; Ye, Z. J. Am. Chem. Soc. 1996, 118, 1801. Marshall, J. A.; Hinkle, K. W. J. Org. Chem. 1996, 61, 4247. Marshall, J. A.; Hinkle, K. W. J. Org. Chem. 1997, 62, 5989. Marshall, J. A.; Chen, M. J. Org. Chem. 1997, 62, 5996.
5. Total syntheses: Hoye, T. R.; Ye, Z. J. Am. Chem. Soc. 1996, 118, 1801. Marshall, J. A.; Hinkle, K. W. J. Org. Chem. 1996, 61, 4247. Marshall, J. A.; Hinkle, K. W. J. Org. Chem. 1997, 62, 5989. Marshall, J. A.; Chen, M. J. Org. Chem. 1997, 62, 5996.
6. Total syntheses: Hoye, T. R.; Ye, Z. J. Am. Chem. Soc. 1996, 118, 1801. Marshall, J. A.; Hinkle, K. W. J. Org. Chem. 1996, 61, 4247. Marshall, J. A.; Hinkle, K. W. J. Org. Chem. 1997, 62, 5989. Marshall, J. A.; Chen, M. J. Org. Chem. 1997, 62, 5996.
7. Total syntheses: Hoye, T. R.; Ye, Z. J. Am. Chem. Soc. 1996, 118, 1801. Marshall, J. A.; Hinkle, K. W. J. Org. Chem. 1996, 61, 4247. Marshall, J. A.; Hinkle, K. W. J. Org. Chem. 1997, 62, 5989. Marshall, J. A.; Chen, M. J. Org. Chem. 1997, 62, 5996.
8. Sinha, S. C.; Sinha, A.; Yazbak, A.; Keinan, E. J. Org. Chem. 1996, 61, 7640 and previous papers cited therein.
9. (a) Casiraghi, G.; Rassu, G. Synthesis 1995, 607.
10. (b) Casiraghi, G.; Zanardi, F.; Rassu, G.; Spanu, P. Chem. Rev. 1995, 95, 1677.
11. Rassu, G.; Zanardi, F.; Battistini, L.; Gaetani, E.; Casiraghi, G. J. Med. Chem. 1997, 40, 168.
12. Rassu, G.; Pinna, L.; Spanu, P.; Zanardi, F.; Battistini, L.; Casiraghi, G. J. Org. Chem. 1997, 62, 4513.
13. (e) Hanessian, S.; McNaughton-Smith, G. Bioorg. Med. Chem. Lett. 1996, 6, 1567.
14. (f) Hanessian, S.; Raghavan, S. Bioorg. Med. Chem. Lett. 1994, 4, 1697.
15. (g) Pichon, M.; Figadère, B.; Cavé, A. Tetrahedron Lett. 1996, 37, 7963.
16. Concurrent with ourselves, the group of Figadère developed a similar (silyloxy)furan-based approach, where the scope was limited to assembly of "natural" oligo-THF motifs. See: Figadère, B.; Peyrat, J.-F.; Cavè, A. J. Org. Chem. 1997, 62, 3428.
17. The enantiomeric excesses of 2a-c were judged to be 96%, 92%, and 98%, respectively, based on Mosher ester analyses of suitable hydroxymethyl intermediates. See ref 5c.
18. This coupling maneuver can be regarded as a C-glycosylation reaction, with the silyloxy dienes as acceptors and lactols as donors.
19. For dinuclear compounds listed in Chart 1, we opted to utilize an immediately explicative naming based on the heteroatom composition and stereochemistry instead of the usual arabic numbering.
20. As a rule, (4R)-configured 2,3-unsaturated butenolides and relative compounds are dextrorotatory, while (4S)-configured counterparts are levorotatory. See: Casiraghi, G.; Colombo, L.; Rassu, G.; Spanu, P.; Gasparri Fava, G.; Ferrari Belicchi, M. Tetrahedron 1990, 46, 5807.
21. 4,5-Erythro butenolides and congeners were also distinguished from their 4,5-threo counterparts by the downfield chemical shift of the H-3 proton. See: Jefford, C. W.; Jaggi, D.; Boukouvalas, J. Tetrahedron Lett. 1987, 28, 4037. Figadère, B.; Chaboche, C.; Peyrat, J.-F.; Cavé, A. Tetrahedron Lett. 1993, 34, 8093.
22. 4,5-Erythro butenolides and congeners were also distinguished from their 4,5-threo counterparts by the downfield chemical shift of the H-3 proton. See: Jefford, C. W.; Jaggi, D.; Boukouvalas, J. Tetrahedron Lett. 1987, 28, 4037. Figadère, B.; Chaboche, C.; Peyrat, J.-F.; Cavé, A. Tetrahedron Lett. 1993, 34, 8093.
23. The H-4-H-5 anti disposition was found to be energetically favorable for the erythro isomers, as compared to the threo ones, and this behavior was magnified for S,S-derivatives. For some representative dinuclear fragments (X, X' = O,O and S,S), a molecular mechanics calculation was performed (Sybyl 6.3, Tripos Inc. St. Louis MO), simulating a rotation around the C-4-C-5 bond. The calculation of the relative populations of anti and gauche conformations allowed the prediction of the mean J values, which were in good accordance with the experimental ones, thus confirming the discussed assignments. In particular, the calculated and observed J values were: 4,5-threo-O,O: 4.4 Hz (obsd 2.5 Hz), 4,5-erythro-O,O: 6.4(6.1), 4,5-threo-S,S: 7.7 (8.3), 4,5-erythro-S,S: 9.8 (10.5).