Photo-/electro-chemical catalysis: a promising toolkit for late-stage functionalization of alkene-containing natural products.

Abstract

Covering: 2013 to 2024Alkene-containing natural products (NPs) are abundantly present in plants, animals, and microorganisms. Strategic alkene modification of NPs not only generates diverse chemical libraries, enriching scaffold, stereochemistry and appendage variations but also aids in unraveling the intricate mechanisms and cellular targets of NPs. Over the past 15 years, visible-light photocatalysis and electrochemical catalysis have emerged as two highly promising approaches for novel chemical transformations. It is worth emphasizing that these radical-mediated strategies have indeed altered the conventional transformation patterns of alkenes. These electronic or energy supply methods reduce dependence on stringent reaction conditions, showcasing more green and efficient characteristics. Over the years, numerous articles have been published, providing concise summaries of remarkable advancements in the fields of photo-organic synthesis, electro-organic synthesis, and late-stage functionalization (LSF). These contributions have predominantly centered on mechanistic explorations of chemical reactivity, with comparatively less emphasis on leveraging these transformations for the LSF of NPs to probe their biological functions. This review is organized according to the reaction types of alkenes, and we aim to elucidate the pathways for the LSF of NPs, exploring their synthetic potential and delineating the limitations of specific reaction classes. Through this overview, we expect that function-oriented synthetic methodologies will drive future research directions, facilitating mutual feedback and collaboration between synthetic chemistry, medicinal chemistry and chemical biology.