Carbon carbon bond forming reactions are essentially important for the fiend of organic chemistry. Specifically, methods that employ readily available starting materials such as carbonyls and olefins are of particular utility. Furthermore, new methods need to be developed that avoid precious transition metals. Exploration of these new and improved methods will continue to drive organic synthesis forward to greater discoveries and applications. We herein report a new mode of reactivity between carbonyls and olefins that departs from the traditional carbonyl ene, Prins, and carbonyl olefin metathesis reactions. Additionally, this Bronsted acid catalyzed transformation has been applied to the synthesis of a wide variety of polycyclic ring systems found in an assortment of biologically active natural products, pharmaceuticals, and materials. The complete substrate scope of the transformation, with variation of each part of the starting material, will be shown. The demonstrated application of this method will also be discussed towards fluxional materials and pharmaceutical analog synthesis. Thorough experimental and computational studies have also been undertaken to explore the mechanism of this new transformation. A proposed mechanism for the transformation will be put forward that encompasses the entirety of this information. From the isolation of intermediates and reaction monitoring experiments to theoretical simulations of the reaction potential energy surface data will be presented to support our proposed mechanism. Lastly, implications of this new method and what can be learned going forward will be discussed.

Interrupted carbonyl olefin metathesis reaction via oxygen atom transfer

256th National Meeting (2018)

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