Radicals by Design

Abstract

Radical reactions offer many advantages over conventional chemical reactions, lending themselves to numerous bond forming processes and rearrangements that are, clean, rapid, and tolerant of a wide range of functional groups. This review provides a brief overview of the design concepts behind new reactions illustrating, in particular, their relevance for the efficient synthesis of biomolecules. Tw o general reactions are highlighted: single electron transfer (SET) using SmI 2 and hydrogen transfer using reagents such as those based on tin, thiols and phosphorous reagents. Intermolecular influences that may direct radical reactions, such as partial protonation and radical complexation, are also discussed.

If It Is Hard, It Is Worth Doing: Engineering Radical Enzymes from Anaerobes

“…There is a recognized need within the pharmaceutical industry for efficient functionalization reactions, 1 , 2 including late-stage C–H functionalization and C–C bond formation, 3 , 4 that can be cleanly delivered by radical chemistry. 5 Radical enzymes, in particular, offer a mechanism by which such transformations can potentially be sustainably embedded into synthetic industrial processes through a biotechnological approach. An added benefit is that these enzymes often already act on molecules of biochemical/medical interest, such as sugars, peptides, and nucleotides.…”