Single-atom skeletal editing has recently emerged as a powerful strategy for the direct diversification of the heterocyclic cores of various compounds. Yet, methods that enable monocycle-to-bicycle tr...

Despite recent advances in primary sulfonamide synthesis, approaches using primary amines as starting points for direct sulfonamide construction remain elusive. Now a formal SO2 insertion into the C–N...

Divergent synthesis is a powerful strategy that provides simultaneous access to multiple derivatives of a given substrate. However, the emerging developments in skeletal editing have largely delivered...

Heteroaromatics are the basis for many pharmaceuticals. The ability to modify these structures through selective core-atom transformations, or “skeletal edits”, can dramatically expand the landscape f...

Herein, we report a detailed investigation of the photomediated transformation of indazoles to benzimidazoles through a nitrogen-carbon transposition. This phototransposition is known to occur in low....

The prevalence of saturated azacycles within pharmaceuticals, natural products, and agrochemicals has prompted the development of many methods that modify their periphery. In contrast, technologies th...

We recently reported a chiral phosphoric acid (CPA) catalyzed enantioselective photomediated ring contraction of piperidines and other saturated heterocycles. By extruding a single heteroatom from a r...

Herein, we introduce a new platform for alkene carboxy-alkylation. This reaction is designed around CO2•– addition to alkenes followed by radical polar crossover, which enables alkylation through carbanion attack on carbonyl electrophiles. We discovered that CO2•– adds to alkenes faster than it reduces carbonyl electrophiles and that this reactivity can be exploited by accessing CO2•– via hydrogen atom transfer from formate. This photocatalytic system transforms vinylarenes and carbonyl compounds into a diverse array of substituted γ-lactone products. Furthermore, indoles can be engaged through dearomative carboxy-alkylation, delivering medicinally relevant C(sp3)-rich heterocyclic scaffolds. Mechanistic studies reveal that the active photocatalyst is generated in situ through a photochemically induced reaction between the precatalyst and DMSO. Overall, we have developed a three-component alkene carboxy-alkylation reaction enabled by the use of formate as the CO2•– precursor.

A 3-step modular procedure combining carboxylic acids with acyl hydrazines provides access to medicinally relevant [1,2,4]-fused triazoles. Good to excellent yields are achieved with tolerance of alip...

4′-Thionucleosides (thNAs) are synthetic nucleoside analogues that have attracted attention as leads for drug discovery in oncology and virology. Here we report a de novo thNA synthesis that relies on...

Heteroaromatics are the basis for many pharmaceuticals. The ability to modify these structures through selective core-atom transformations, or "skeletal edits", can dramatically expand the landscape f...

The functionalization of C–H bonds enables the modification of complex molecules, often with the intention of forming compound libraries. The borylation of aryl C–H bonds is a widely used class of C–H...