Ru-catalyzed olefin metathesis, an exceptionally versatile means of constructing new carbon–carbon bonds, has transformed organic synthesis in academia. Groundbreaking advances enabled by the N-heterocyclic carbene–stabilized, “second-generation” Ru catalysts (e.g. GII, HII; Chart 1) range from the RCM assembly of recent blockbuster hepatitis C virus therapeutics to the elaboration of renewable plant oils into value-added products and chemicals. Important limitations, however, arise from catalyst decomposition. Notwithstanding an abundance of studies on the synthesis of new catalysts, and on the decomposition processes operative for the inactive, off-cycle species, the fundamental principles that govern activity and decomposition for the active, on-cycle intermediates (e.g. Ru-1, Ru-2; Chart 1) have been surprisingly little examined. A key reason for this is their high reactivity, which makes them elusive targets for study. Nonetheless, such understanding is an essential tool for informed catalyst and process redesign. Here we discuss recent insights into the reactivity and decomposition of active intermediates in metathesis, with emphasis placed on fundamental principles, and some solutions.

Following the catalyst wherever she goes: Forays into the fundamental behavior of active, on-cycle intermediates in Ru-catalyzed olefin metathesis

2019 Fall National Meeting

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