Catalytic remodeling of complex alkenes to oxonitriles through C=C double bond deconstruction.

Deconstructive transformation of carbon-carbon double bonds (C=C) is a pivotal strategy in synthetic chemistry and drug discovery. Despite the substantial advances in olefin metathesis and ozonolysis for natural product synthesis through C=C double-bond cleavage, the catalytic remodeling of complex molecules through C=C double-bond deconstruction has been underdeveloped. We report a heterogeneous copper-catalyzed C=C double-bond cleavage, which enables the remodeling of complex molecules by converting the carbons on either side of the C=C double bond to carbonyl and cyano groups, respectively. In particular, this method provides an efficient protocol to conveniently transform terpenoids, glycals, steroids, and bioactive molecules to privileged scaffolds with underexplored chemical space. Editor's summary: Carbon-nitrogen bonds are cornerstones of modern pharmaceuticals, and chemists continually strive to find more efficient ways to make them. Two studies now report distinct methods of cleaving carbon-carbon double bonds and forming carbon-nitrogen triple bonds in their place. Brägger et al. used a hypervalent iodine reagent to produce the nitrile products, whereas Cheng et al. used a heterogeneous copper catalyst in conjunction with oxygen. In both cases, the carbon-carbon double bonds served as convenient handles for the transformation of a wide variety of complex molecules. —Jake S. Yeston [ABSTRACT FROM AUTHOR]