Electrochemically Driven Hydrogen Atom Transfer Catalysis: A Tool for C(sp3)/Si-H Functionalization and Hydrofunctionalization of Alkenes

Electrochemically driven hydrogen atom transfer (HAT)catalysisprovides a complementary approach for the transformation of redox-inactivesubstrates that would be inaccessible to conventional electron transfer(ET) catalysis. Moreover, electrochemically driven HAT catalysis couldpromote organic transformations with either hydrogen atom abstractionor donation as the key step. It provides a versatile and effectivetool for the direct functionalization of C(sp(3))-H/Si-Hbonds and the hydrofunctionalization of alkenes. Despite these attractiveproperties, electrochemically driven HAT catalysis has been largelyoverlooked due to the lack of understanding of both the catalyticmechanism and how catalyst selection should occur. In this Review,we give an overview of the HAT catalysis applications in the directC(sp(3))-H/Si-H functionalization and hydrofunctionalizationof alkenes. The mechanistic pathways, physical properties of the HATmediators, and state-of-the-art examples are described and discussed.

Automated summary

Electrochemically driven hydrogen atom transfer (HAT) catalysis is a versatile and effective tool for the transformation of redox-inactive substrates and the functionalization of C(sp(3))-H/Si-H bonds and alkenes. However, its potential has been largely overlooked due to a lack of understanding of its catalytic mechanism and catalyst selection. In this Review, an overview of HAT catalysis applications, mechanistic pathways, physical properties of HAT mediators, and state-of-the-art examples are provided and discussed.