Stephen J Harwood, Maximilian D Palkowitz, Cara N. Gannett
Feb 18, 2022
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Influential Citations
30
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Journal
Science
Abstract
The synthesis of terpenes is a large field of research that is woven deeply into the history of chemistry. Terpene biosynthesis is a case study of how the logic of a modular design can lead to diverse structures with unparalleled efficiency. This work leverages modern nickel-catalyzed electrochemical sp2–sp3 decarboxylative coupling reactions, enabled by silver nanoparticle–modified electrodes, to intuitively assemble terpene natural products and complex polyenes by using simple modular building blocks. The step change in efficiency of this approach is exemplified through the scalable preparation of 13 complex terpenes, which minimized protecting group manipulations, functional group interconversions, and redox fluctuations. The mechanistic aspects of the essential functionalized electrodes are studied in depth through a variety of spectroscopic and analytical techniques. Description Charging up terpene synthesis A recent strategy for forming carbon–carbon bonds involves the reaction of a redox-active ester with an organometallic coupling partner. This approach suffers from the sensitivity of various functional groups in addition to the ester to the organometallic. Harwood et al. report a versatile electrochemical approach, paired with nickel catalysis, that avoids the organometallic. Modification of the electrode with silver nanoparticles proved key to the method’s broad applicability, which the authors showcased across a range of total and formal terpene natural product syntheses. —JSY Modifying electrodes with silver nanoparticles is broadly enabling for electrochemical formation of carbon–carbon bonds.