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  Total Syntheses of the Phytotoxic Lactones Herbarumin I and II and a Synthesis-Based Solution of the Pinolidoxin Puzzle

Fürstner, A., Radkowski, K., Wirtz, C., Goddard, R., Lehmann, C. W., & Mynott, R. (2002). Total Syntheses of the Phytotoxic Lactones Herbarumin I and II and a Synthesis-Based Solution of the Pinolidoxin Puzzle. Journal of the American Chemical Society, 124(24), 7061-7069. doi:10.1021/ja020238i.

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 Creators:
Fürstner, Alois1, Author           
Radkowski, Karin1, Author           
Wirtz, Conny2, Author           
Goddard, Richard3, Author           
Lehmann, Christian W.3, Author           
Mynott, Richard4, Author           
Affiliations:
1Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445584              
2Service Department Farès (NMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445623              
3Service Department Lehmann (EMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445625              
4Service Department Mynott (NMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445627              

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 Abstract: A concise approach to a family of potent herbicidal 10-membered lactones is described on the basis of ring-closing metathesis (RCM) as the key step for the formation of the medium-sized ring. This includes the first total syntheses of herbarumin I (1) and II (2) as well as the synthesis of several possible macrolides of the pinolidoxin series, A comparison of their spectral and analytical data with those of the natural product allowed us to establish the stereostructure of pinolidoxin, a potent inhibitor of induced phenylalanine ammonia lyase (PAL) activity, as shown in 46. This finding, however, makes clear that a previous study dealing with the relative and absolute stereochemistry of this phytotoxic agent cannot be correct. An important aspect from the preparative point of view is the fact that the stereochemical outcome of the RCM reaction can be controlled by the choice of the catalyst. Thus, use of the ruthenium indenylidene complex 16 always leads to the corresponding (E)-alkenes, whereas the second generation catalyst 17 bearing an N-heterocyclic carbene ligand affords the isomeric (2)-olefin with good selectivity. This course is deemed to reflect kinetic versus thermodynamic control of the cyclization reaction and therefore has potentially broader ramifications for the synthesis of medium-sized rings in general. A further noteworthy design feature is the fact that D-ribose is used as a convenient starting material for the preparation of both enantiomers of the key building block 14 by means of a "head-to-tail" interconversion strategy.

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Language(s): eng - English
 Dates: 2002-02-152002-05-222002-06-01
 Publication Status: Published in print
 Pages: 9
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/ja020238i
 Degree: -

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Title: Journal of the American Chemical Society
  Other : JACS
  Abbreviation : J. Am. Chem. Soc.
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 124 (24) Sequence Number: - Start / End Page: 7061 - 7069 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870