The first report of Z-selective macrocyclizations using a ruthenium-based metathesis catalyst is described. Selectivity for Z--macrocycles is consistently high for a diverse set of substrates bearing different functional groups and comprised of various ring sizes. The same catalyst was employed for the Z-selective ethenolysis of a mixture of E and Z macrocycles, providing the pure E-isomers. These methodologies were successfully applied to the construction of several olfactory macrocycles, as well as the backbone of cytotoxic alkaloid natural products. Conditions were also optimized for a series of challenging cross metathesis reactions using the same catalyst system, and subsequently exploited in the synthesis of a family of lepidopteran insect pheromones. A detailed mechanistic study probing the origin of the stereoselectivity in these challenging transformations is currently underway, and will also be discussed in detail.

Synthetic applications of Z-selective ruthenium-based olefin metathesis catalysts

245th National Meeting (2013)

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