RESUMEN
While attempting to synthesize biaryl ethers we discovered the inadvertent formation of a methylsulfoxylmethyl ether byproduct. Formation of this unexpected byproduct presented an opportunity to streamline the synthesis of methylsulfoxylmethyl ethers. Mechanistic studies suggest a radical pathway with dimsyl potassium as a reducing agent.
RESUMEN
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. The discovery of the photoredox mediated generation of chlorine atoms with Ir-based polypyridyl complex, [Ir(dF(CF3 )ppy)2 (dtbbpy)]Cl, under blue LED irradiation is reported.
RESUMEN
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, [Au2(dppm)2]Cl2.