Correlation between Functionality Preference of Ru Carbenes and <i>exo</i>/<i>endo</i> Product Selectivity for Clarifying the Mechanism of Ring-Closing Enyne Metathesis

Functionality preferences of metathesis Ru carbenes to various alkenes and alkynes with electronic and steric diversity were determined by using time-dependent fluorescence quenching. The functionality preferences depend not only on the properties of multiple bonds but also on the ligands on Ru. There was a good correlation between functionality preference and the metathesis reaction outcome. The correlation between functionality preference and <i>exo</i>/<i>endo</i> product ratio offers a solution to resolve the mechanistic issue related with alkene- vs alkyne-initiated pathway in ring-closing enyne metathesis. The correlation indicates the preference is likely to dictate the reaction pathway and eventually the outcome of the reaction. The Ru catalyst favoring alkyne over alkene provides more <i>endo</i> product, indicating that the reaction mainly initiates at the alkyne. By changing the substitution pattern, the preference can be reversed to give an exclusive <i>exo</i> product

Preference of Ruthenium-Based Metathesis Catalysts toward <i>Z</i>- and <i>E</i>‑Alkenes as a Guide for Selective Reactions to Alkene Stereoisomers

As a guide for selective reactions toward either <i>Z</i>- or <i>E</i>-alkene in a metathesis reaction, the relative preference of metathesis Ru catalysts for each stereoisomer was determined by a method using time-dependent fluorescence quenching. We found that <b>Ru-1</b> prefers the <i>Z</i>-isomer over the <i>E</i>-isomer, whereas <b>Ru-2</b> prefers the <i>E</i>-isomer over the <i>Z</i>-isomer. The <i>Z</i>/<i>E</i>-alkene preference of the catalysts precisely predicted the <i>Z</i>/<i>E</i> isomeric selectivity in the metathesis reactions of diene substrates possessing combinations of <i>Z</i>/<i>E</i>-alkenes. For the diene substrates, the rate order of the reactions using <b>Ru-1</b> was <i>Z,Z-</i>1,6-diene > <i>Z,E-</i>1,6-diene > <i>E,E-</i>1,6-diene, while the completely opposite order of <i>E,E-</i>1,6-diene > <i>Z,E-</i>1,6-diene > <i>Z,Z-</i>1,6-diene was exhibited in the case of <b>Ru-2</b>