Fast-Initiating, Ruthenium-based Catalysts for Improved Activity in Highly E‑Selective Cross Metathesis

Ruthenium-based olefin metathesis catalysts bearing dithiolate ligands have been recently employed to generate olefins with high E-selectivity (>99% E) but have been limited by low to moderate yields. In this report, 1H NMR studies reveal that a major contributing factor to this low activity is t...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2017-02, Vol.139 (4), p.1532-1537
Main Authors: Ahmed, Tonia S, Grubbs, Robert H
Format: Article
Language:English
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Summary:Ruthenium-based olefin metathesis catalysts bearing dithiolate ligands have been recently employed to generate olefins with high E-selectivity (>99% E) but have been limited by low to moderate yields. In this report, 1H NMR studies reveal that a major contributing factor to this low activity is the extremely low initiation rates of these catalysts with trans olefins. Introducing a 2-isopropoxy-3-phenylbenzylidene ligand in place of the conventional 2-isopropoxy­benzylidene ligand resulted in catalysts that initiate rapidly under reaction conditions. As a result, reactions were completed in significantly less time and delivered higher yields than those in previous reports while maintaining high stereoselectivity (>99% E).
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.6b11330