A biomimetic route to the peptide alkaloid anachelin

Angewandte Chemie - International Edition

Volumn 43, Issue 25, 2004, Pages 3327-3329

  Gademann, Karl ^a   Bethuel, Yann ^a  

^a ETH ZURICH   (Switzerland)

Author keywords

Alkaloids; Biomimetic syntheses; Natural products; Peptides; Polyketides

Indexed keywords

CONDENSATION; GENES; OXIDATION; SUBSTRATES; SYNTHESIS (CHEMICAL);

ALKALOID ANACHELIN; ANNULATION;

POLYPEPTIDES;

ALKALOID DERIVATIVE; ANACHELIN; PEPTIDE; UNCLASSIFIED DRUG;

ALDOL REACTION; ARTICLE; BIOMIMETICS; BIOTRANSFORMATION; CHROMATOGRAPHY; CLAISEN CONDENSATION; DEPROTECTION REACTION; ISOMERISM; OXIDATION; PURIFICATION; REDUCTION;

ALKALOIDS; BIOMIMETICS; MOLECULAR CONFORMATION; OLIGOPEPTIDES; PEPTIDES; QUINOLINIUM COMPOUNDS;

EID: 4544386004     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200453909     Document Type: Article

References (19)

1. H. Beiderbeck, K. Taraz, H. Budzikiewicz, A. E. Walsby, Z. Naturforsch. C 2000, 55, 681-687; H. Beiderbeck, Dissertation, Universität Köln, Germany, 2000.
2. H. Beiderbeck, K. Taraz, H. Budzikiewicz, A. E. Walsby, Z. Naturforsch. C 2000, 55, 681-687; H. Beiderbeck, Dissertation, Universität Köln, Germany, 2000.
3. Y. Itou, S. Okada, M. Murakami, Tetrahedron 2001, 57, 9093-9099. This group did not isolate anachelin H (1), but instead two esters isomeric to 1 of the salicylic acid with C(5)-O and C(7)-O of the ε-amino acid of anachelin.
4. This amino acid is only to be found in the peptide antibiotic galantin. Isolation: J. Shoji, R. Sakazaki, Y. Wakisaka, K. Koizumi, M. Mayama, S. Matsuura, J. Antibiot. 1975, 28, 122-125; First synthesis: N. Sakai, Y. Ohfune, J. Am. Chem. Soc. 1992, 114, 998-1010.
5. This amino acid is only to be found in the peptide antibiotic galantin. Isolation: J. Shoji, R. Sakazaki, Y. Wakisaka, K. Koizumi, M. Mayama, S. Matsuura, J. Antibiot. 1975, 28, 122-125; First synthesis: N. Sakai, Y. Ohfune, J. Am. Chem. Soc. 1992, 114, 998-1010.
6. Compound 2 can be transformed by hydrolysis of the oxazoline ring into 1 (see [1]). Therefore, we assume that anachelin H is the more stable compound in the extracellular aquatic environment of A. cylindrica.
7. The transformation B→C is analogous to the biosynthesis of cyclo-DOPA starting from L-DOPA, important intermediates in the biogenesis of betanidin and the melanins.
8. Experimental procedures and analytical data of all new compounds are reported in the Supporting Information and can be obtained from http://www.angewandte.org or from the corresponding author.
9. We did not observe acylation of the aromatic hydroxy groups, as no corresponding by-products could be isolated.
10. The Boc group is not stable under the conditions of the borane reduction.
11. S. V. Ley, C. A. Meerholz, D. H. R. Barton, Tetrahedron 1981, 37, 213-223; for a related application, see J. Clews, C. J. Cooksey, P. J. Garratt, E. J. Land, C. A. Ramsden P. A. Riley, J. Chem. Soc. Perkin Trans. 1 2000, 4306-4315.
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16. The diastereoisomers were separated by crystallization. The relative configuration of 13 was assigned after derivatization to the N,O-acetal using the method of Joullié: B. D. Harris, M. M. Joullié, Tetrahedron 1988, 44, 3489-3500.
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18. We thank Prof. Dr. H. Budzikiewicz for an authentic sample of natural anachelin H.
19. -1).