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

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http://pubman.mpdl.mpg.de/cone/persons/resource/persons58380

Fürstner,  Alois
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons58907

Radkowski,  Karin
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons58881

Peters,  Hartwig
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons58992

Seidel,  Günter
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons59119

Wirtz,  Cornelia
Service Department Mynott (NMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons58838

Mynott,  Richard
Service Department Mynott (NMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons58744

Lehmann,  Christian W.
Service Department Lehmann (EMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

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.


Cite as: http://hdl.handle.net/11858/00-001M-0000-0025-AD31-5
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.