- USING STEREORETENTION FOR THE SYNTHESIS OF E-MACROCYCLES WITH RUTHENIUM-BASED OLEFIN METATHESIS CATALYSTS
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This invention relates generally to the synthesis of E-macrocycles using stereoretentive ruthenium olefin metathesis catalysts supported by dithioiate ligands. Macrocycles were generated with excellent selectivity (>99% E) and in moderate to high/good yields (47% to 80% yield; 58% to 80% yield) from diene starting materials bearing two E-olefins or bearing one E- olefin and one terminal olefin, A variety of rings were constructed, ranging from 12- to 18- membered macrocycles, including the antibiotic recifeiolide. The invention has utility in the fields of organometallics and organic synthesis.
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Paragraph 198
(2019/06/23)
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- REACTIONS OF OLEFIN DERIVATIVES IN THE PRESENCE OF METATHESIS CATALYSTS
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The invention provides a method for synthesizing musk macrocycles comprising contacting an easily accessible diene starting materials bearing a Z-olefin moiety and performing a ring closing metathesis reaction in the presence of a Group 8 olefin metathesi
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Paragraph 000153
(2019/09/04)
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- A HIGHLY EFFICIENT SYNTHESIS OF Z-MACROCYCLES USING STEREORETENTIVE, RUTHENIUM-BASED METATHESIS CATALYSTS
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A highly efficient, Z-selective ring-closing metathesis system for the formation of macrocycles using a stereoretentive, ruthenium-based catalyst supported by a dithiolate ligand is reported. This catalyst is demonstrated to be remarkably active as observed in initiation experiments showing complete catalyst initiation at - 20°C within 10 min. Using easily accessible diene starting materials bearing a Z-olefin moiety, macrocyclization reactions generated products with significantly higher Z-selectivity in appreciably shorter reaction times, in higher yield, and with much lower catalyst loadings than in previously reported systems. Macrocyclic lactones ranging in size from twelve-mem bered to seventeen-membered rings are synthesized in moderate to high yields (68 - 79% yield) with excellent Z-selectivity (95% - 99% Z).
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Page/Page column 44
(2018/12/02)
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- A Highly Efficient Synthesis of Z-Macrocycles Using Stereoretentive, Ruthenium-Based Metathesis Catalysts
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A highly efficient, Z-selective ring-closing metathesis system for the formation of macrocycles using a stereoretentive, ruthenium-based catalyst supported by a dithiolate ligand is reported. The catalyst is remarkably active as observed in initiation experiments showing complete catalyst initiation at ?20 °C within 10 minutes. Macrocyclization reactions generated Z-products from easily accessible diene starting materials bearing a Z-olefin moiety. This approach provides a more efficient and selective route to Z-macrocycles relative to previously reported systems. Reactions were completed within shorter reaction times, and turnover numbers of up to 100 could be achieved. Macrocyclic lactones ranging in size from twelve- to seventeen-membered rings were synthesized in moderate to high yields (67–79 %) with excellent Z-selectivity (95–99 %).
- Ahmed, Tonia S.,Grubbs, Robert H.
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supporting information
p. 11213 - 11216
(2017/09/02)
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