ABSTRACT
This review highlights the history and recent advances in dealkenylative functionalization. Through this deconstructive strategy, radical functionalizations occur under mild, robust conditions. The reactions described proceed with high efficiency, good stereoselectivity, tolerate many functional groups, and are completed within a matter of minutes. By cleaving the C(sp3)-C(sp2) bond of terpenes and terpenoid-derived precursors, rapid diversification of natural products is possible.
ABSTRACT
Organic peroxides are becoming popular intermediates for novel chemical transformations. The weak O-O bond is readily reduced by transition metals, including iron and copper, to initiate a radical cascade process that breaks C-C bonds. Great potential exists for the rapid generation of complexity, originating from the ability to couple the resulting free radicals with a wide range of partners. First, this review article discusses the history and synthesis of organic peroxides, providing the context necessary to understand this methodology. Then, it highlights 91 examples of recent applications of the radical functionalization of C-C bonds accessed through the transition metal-mediated reduction of organic peroxides. Finally, we provide some comments about safety when working with organic peroxides.