Molybdenum and tungsten monoaryloxide pyrrolide (MAP) alkylidene complexes catalyze the Z-selective metathesis homocoupling of (E)-1,3-diene substrates to give (E,Z,E) conjugated trienes in high yield. The most effective catalysts highly prefer reaction with the terminal alkene functionality of the dienes, limiting the formation of unwanted side products. Cross metathesis of (E)-1,3-dienes with various olefinic substrates (including vinyl ethers) using the same catalyst systems selectively furnishes products containing the (E,Z) conjugated diene motif. These reactions proceed through unusual alkylidene intermediates, such as vinylalkylidenes and alkoxyalkylidenes. Isolation and characterization of vinylalkylidene and alkoxyalkylidene MAP species are reported along with investigations of their stability and reactivity.

Highly <i>Z</i>-selective and chemoselective olefin metathesis of 1,3-dienes: Catalytic studies and exploration of unusual intermediates

245th National Meeting (2013)

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Highly Z-selective and chemoselective olefin metathesis of 1,3-dienes: Catalytic studies and exploration of unusual intermediates