Electrochemically Enabled Total Syntheses of Natural Products

Abstract

Electrochemical techniques have helped to enable the total synthesis of natural products since the pioneering work of Kolbe in the mid 1800’s. The electrochemical toolset grows every day and these new possibilities change the way chemists look at and think about natural products. This review provides a perspective on total syntheses wherein electrochemical techniques enabled the carbon‐carbon bond formations in the skeletal assembly of important natural products, discussion of mechanistic details, and representative examples of the bond formations enabled over the last several decades. These bond formations are often distinctly different from those possible with conventional chemistries and allow assemblies complementary to other techniques.

Reductive cyclodimerization of chalcones: exploring the “self-adaptability” of galvanostatic electrosynthesis

“…The use of synthetic organic electrochemistry (electroChem) not only replaces stoichiometric oxidizing/reducing chemical agents with electrons as traceless equivalents, but also delivers novel reaction pathways and complementary selectivity. 2 In this scenario, the peculiar features of galvanostatic electrolysis offer a reaction manifold of unparalleled power and simplicity. 3 Self-adapting the reaction potential to the one that is needed for the less demanding process to occur allows for the precise control of cascade processes, even where the subsequent reactive events are energetically more demanding than the previous ones (Fig.…”

Hole Catalysis of Cycloaddition Reactions: How to Activate and Control Oxidant Upconversion in Radical-Cationic Diels–Alder Reactions

“…By understanding the simple logic of upconversion, we can design reactions where true hole-catalyzed pathways are exploited reliably by restoring the oxidative potential of the hole in each reaction cycle. We hope that such rational design will help the development of the burgeoning fields of organic electrochemistry − and photoredox catalysis. , …”

Synthetic Access to 1,3-Butadiynes via Electro-redox Cuprous-Catalyzed Dehydrogenative Csp–Csp Homocoupling of Terminal Acetylenes

“…10 Thanks to this eco-friendly nature, electro-organic synthesis has been successfully applied to generate an array of synthetic 11 and natural compounds. 12 Electrosynthesis has the advantage of selectively oxidizing or reducing organic molecules within a wide potential window, thereby granting access to regio/chemoselective synthesis. 13 Notably, functional group tolerance under electrochemical conditions accommodates a range of substrates, which in turn opens up possibilities for transforming reactive functionalities under mild conditions.…”