The opportunity to activate C(sp3)−H bonds via homolytic cleavage by means of halogen radicals has long been disregarded in synthetic endeavors due to the unpredictable selectivity. Nowadays, photocatalysis has established itself as a method of choice for the generation of such reactive intermediates under mild conditions. This Minireview collects recent examples showcasing how photocatalytic manifolds have been used to tame aggressive halogen radicals to activate C(sp3)−H bonds via Hydrogen Atom Transfer (HAT) for synthetic purposes. In the last section of this work, we address site‐selectivity issues posed by this methodology and show how it can be guided through the judicious choice of reaction conditions.

The late-stage introduction of allyl groups provides an opportunity to synthetic organic chemists for subsequent diversification, furnishing a rapid access to new chemical space. Here, we report the development of...

An efficient continuous photochemical process is presented that delivers a series of novel γ-aminopropylsulfones via a tetrabutylammonium decatungstate (TBADT) catalysed HAT-process.

The ability to construct C(sp 3 )À C(sp 3 ) bonds from easily accessible reagents is a crucial, yet challenging endeavor for synthetic organic chemists. Herein, we report the realization of such a cross-coupling reaction, which combines N-sulfonyl hydrazones and C(sp 3 )À H donors through a diarylketone-enabled photocatalytic hydrogen atom transfer and a subsequent fragmentation of the obtained alkylated hydrazide. This mild and metal-free protocol was employed to prepare a wide array of alkyl-alkyl cross-coupled products and is tolerant of a variety of functional groups. The application of this chemistry further provides a preparatively useful route to various medicinally-relevant compounds, such as homobenzylic ethers, aryl ethyl amines, β-amino acids and other moieties which are commonly encountered in approved pharmaceuticals, agrochemicals and natural products.

The late-stage introduction of allyl groups provides an opportunity to synthetic organic chemists for subsequent diversification, providing rapid access to new chemical space. Here, we report the development of a modular synthetic sequence for the allylation of strong aliphatic C(sp3)–H bonds. Our sequence features the merger of two distinct steps to accomplish this goal, including a photocatalytic Hydrogen Atom Transfer and an ensuing Horner-Wadsworth-Emmons reaction. This practical protocol enables the modular and scalable allylation of valuable building blocks and medicinally relevant molecules.