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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

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

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

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

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

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Ilg,  Marina Kristina
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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

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

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Citation

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.


Cite as: http://hdl.handle.net/11858/00-001M-0000-002A-F007-E
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.