Redox-Neutral Multicatalytic Cerium Photoredox-Enabled Cleavage of O-H Bearing Substrates.

The need for synthetic methodologies capable of rapidly altering molecular structure are in high demand. Most existing methods to modify scaffolds rely on net exothermicity to drive the desired transformation. We sought to develop a general strategy for the cleavage of C-C bonds β to hydroxyl groups independent of inherent substrate strain.

Hydrogen Atom Transfer Reactions via Photoredox Catalyzed Chlorine Atom Generation.

The selective functionalization of chemically inert C-H bonds remains to be fully realized in achieving organic transformations that are redox-neutral, waste-limiting, and atom-economical. The catalytic generation of chlorine atoms from chloride ions is one of the most challenging redox processes, where the requirement of harsh and oxidizing reaction conditions renders it seldom utilized in synthetic applications. We report the mild, controlled, and catalytic generation of chlorine atoms as a new opportunity for access to a wide variety of hydrogen atom transfer (HAT) reactions owing to the high stability of HCl.

Transformations of Isonitriles with Bromoalkanes Using Photoredox Gold Catalysis.

Isonitriles have excellent electronic compatibility to react with free radicals. Recently, photoredox catalysis has emerged as a powerful tool for the construction of C-C bonds with few protocols for alkylative heterocycle synthesis through isonitrile addition. Herein, we describe the photocatalytic generation of alkyl radicals from unactivated bromoalkanes as part of an efficient cross-coupling strategy for the diversification of isonitriles using a dimeric gold(I) photoredox catalyst, [Au(dppm)]Cl.