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  A Two-Component Alkyne Metathesis Catalyst System with an Improved Substrate Scope and Functional Group Tolerance: Development and Applications to Natural Product Synthesis

Schaubach, S., Gebauer, K., Ungeheuer, F., Hoffmeister, L., Ilg, M. K., Wirtz, C., et al. (2016). A Two-Component Alkyne Metathesis Catalyst System with an Improved Substrate Scope and Functional Group Tolerance: Development and Applications to Natural Product Synthesis. Chemistry – A European Journal, 22(25), 8494-8507. doi:10.1002/chem.201601163.

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 Creators:
Schaubach, Sebastian1, Author           
Gebauer, Konrad1, Author           
Ungeheuer, Felix1, Author           
Hoffmeister, Laura1, Author           
Ilg, Marina Kristina1, Author           
Wirtz, Cornelia2, 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              

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Free keywords: alkyne metathesis;molybdenum;natural products;propargyl alcohols;redox isomerization
 Abstract: Although molybdenum alkylidyne complexes such as 1 endowed with triarylsilanolate ligands are excellent catalysts for alkyne metathesis, they can encounter limitations when (multiple) protic sites are present in a given substrate and/or when forcing conditions are necessary. In such cases, a catalyst formed in situ upon mixing of the trisamidomolybenum alkylidyne complex 3 and the readily available trisilanol derivatives 8 or 11 shows significantly better performance. This two-component system worked well for a series of model compounds comprising primary, secondary or phenolic -OH groups, as well as for a set of challenging (bis)propargylic substrates. Its remarkable efficiency is also evident from applications to the total syntheses of manshurolide, a highly strained sesquiterpene lactone with kinase inhibitory activity, and the structurally demanding immunosuppressive cyclodiyne ivorenolide A; in either case, the standard catalyst 1 largely failed to effect the critical macrocyclization, whereas the two-component system was fully operative. A study directed toward the quinolizidine alkaloid lythrancepine I features yet another instructive example, in that a triyne substrate was metathesized with the help of 3/11 such that two of the triple bonds participated in ring closure, while the third one passed uncompromised. As a spin-off of this project, a much improved ruthenium catalyst for the redox isomerization of propargyl alcohols to the corresponding enones was developed.

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Language(s): eng - English
 Dates: 2016-03-112016-05-202016-06-13
 Publication Status: Published in print
 Pages: 14
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1002/chem.201601163
 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: 22 (25) Sequence Number: - Start / End Page: 8494 - 8507 Identifier: ISSN: 0947-6539
CoNE: https://pure.mpg.de/cone/journals/resource/954926979058