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  Catalysis-Based and Protecting-Group-Free Total Syntheses of the Marine Oxylipins Hybridalactone and the Ecklonialactones A, B, and C

Hickmann, V., Kondoh, A., Gabor, B., Alcarazo, M., & Fürstner, A. (2011). Catalysis-Based and Protecting-Group-Free Total Syntheses of the Marine Oxylipins Hybridalactone and the Ecklonialactones A, B, and C. Journal of the American Chemical Society, 133(34), 13471-13480. doi:10.1021/ja204027a.

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ja204027a_si_002.pdf (Supplementary material), 4MB
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Hickmann, Volker1, Author           
Kondoh, Azusa1, Author           
Gabor, Barbara2, Author           
Alcarazo, Manuel3, Author           
Fürstner, Alois1, Author           
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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              
3Research Group Alcarazo, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445592              

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 Abstract: Concise and protecting-group-free total syntheses of the marine oxylipins hybridalactone (1) and three members of the ecklonialactone family (2–4) were developed. They deliver these targets in optically pure form in 14 or 13 steps, respectively, in the longest linear sequence; five of these steps are metal-catalyzed and four others are metal-mediated. The route to either 1 or 2–4 diverges from the common building block 22, which is accessible in 7 steps from 2[5H]furanone by recourse to a rhodium-catalyzed asymmetric 1,4-addition reaction controlled by the carvone-derived diene ligand 35 and a ring-closing alkene metathesis (RCM) catalyzed by the ruthenium indenylidene complex 17 as the key operations. Alternatively, 22 can be made in 10 steps from furfural via a diastereoselective three-component coupling process. The further elaboration of 22 into hybridalactone as the structurally most complex target with seven contiguous chiral centers was based upon a sequence of cyclopropanation followed by a vanadium-catalyzed epoxidation, both of which were directed by the same free hydroxy group at C15. The macrocyclic scaffold was annulated to the headgroup by means of a ring-closing alkyne metathesis reaction (RCAM). In response to the unusually high propensity of the oxirane of the targeted oxylipins for ring opening, this transformation had to be performed with complexes of the type [(Ar3SiO)4Mo≡CPh][K·OEt2] (43), which represent a new generation of exceedingly tolerant yet remarkably efficient catalysts. Their ancillary triarylsilanolate ligands temper the Lewis acidity of the molybdenum center but are not sufficiently nucleophilic to engage in the opening of the fragile epoxide ring. A final semireduction of the cycloalkyne formed in the RCAM step to the required (Z)-alkene completed the total synthesis of (−)-1. The fact that the route from the common fragment 22 to the ecklonialactones could follow a similar logic showcased the flexibility inherent to the chosen approach.

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Language(s): eng - English
 Dates: 2011-05-022011-07-222011-08-31
 Publication Status: Published in print
 Pages: 10
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/ja204027a
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Title: Journal of the American Chemical Society
  Other : J. Am. Chem. Soc.
  Abbreviation : JACS
Source Genre: Journal
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Publ. Info: American Chemical Society
Pages: 10 Volume / Issue: 133 (34) Sequence Number: - Start / End Page: 13471 - 13480 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870