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  Total Synthesis, Molecular Editing and Evaluation of a Tripyrrolic Natural Product: The Case of "Butylcycloheptylprodigiosin"

Fürstner, A., Radkowski, K., Peters, H., Seidel, G., Wirtz, C., Mynott, R., et al. (2007). Total Synthesis, Molecular Editing and Evaluation of a Tripyrrolic Natural Product: The Case of "Butylcycloheptylprodigiosin". Chemistry – A European Journal, 13(7), 1929-1945. doi:10.1002/chem.200601639.

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 Creators:
Fürstner, Alois1, Author           
Radkowski, Karin1, Author           
Peters, Hartwig1, Author           
Seidel, Günter1, Author           
Wirtz, Cornelia2, Author           
Mynott, Richard2, Author           
Lehmann, Christian W.3, Author           
Affiliations:
1Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445584              
2Service Department Mynott (NMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445627              
3Service Department Lehmann (EMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445625              

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Free keywords: alkaloids; DNA cleavage; heterocycles; natural products; palladium; pyrroles
 Abstract: Conflicting reports are found in the literature on whether the ortho-pyrrolophane derivative 6, which has been named “butylcycloheptylprodigiosin” even though it is a cyclononane derivative, is a natural product or merely a mis-assigned structure. This dispute has now been resolved by an unambiguous total synthesis of this complex alkaloid which confirms the initial structure assignment. The chosen approach is largely catalysis-based, featuring the first application of a “Narasaka–Heck” reaction in natural product chemistry. This palladium-catalyzed transformation allows the unsaturated oxime ester 26 to be converted into the bicyclic dihydropyrrole 27. Other notable reactions of the reported approach to 6 are a regioselective Tsuji–Trost reaction of the doubly allylic acetate 21 with methyl acetoacetate, a base-induced aromatization of 27 to the corresponding pyrrole 28, a chemoselective oxidation of the benzylic methyl group in 33 with cerium ammonium nitrate in a biphasic reaction medium that does not affect the labile pyrrole nucleus, and a Suzuki cross-coupling for the completion of the heterocyclic domain. Diversification in the latter step leads to a set of analogues that differ from the natural product in the terminal (hetero)arene ring. This structural modification results in complete loss of the very pronounced ability of the parent compound 6 to induce oxidative cleavage in double stranded DNA in the presence of CuII. Several cyclononane-, cyclononene- and cyclononadiene derivatives prepared en route to 6 have been characterized by crystal structure analysis, allowing the conformational behavior of nine-membered carbocycles to be studied.

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Language(s): eng - English
 Dates: 2006-11-152007-01-162007-02-23
 Publication Status: Published in print
 Pages: 17
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1002/chem.200601639
 Degree: -

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Title: Chemistry – A European Journal
  Other : Chem. – Eur. J.
  Other : Chem. Eur. J.
Source Genre: Journal
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Publ. Info: Weinheim, Germany : VCH Verlagsgesellschaft
Pages: - Volume / Issue: 13 (7) Sequence Number: - Start / End Page: 1929 - 1945 Identifier: ISSN: 0947-6539
CoNE: https://pure.mpg.de/cone/journals/resource/954926979058