2019/05/20 by Balázs Budai, Alexandre Leclair, Qian Wang +1 · 1 citation
Chemistry · #Catalytic C–H Functionalization Methods #Radical Photochemical Reactions #Sulfur-Based Synthesis Techniques
paper · doi:10.1002/ange.201904263
openalex publication_date 2019/05/20 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/23
Abstract Reported here is a copper‐catalyzed 1,2‐methoxy methoxycarbonylation of alkenes by an unprecedented use of methyl formate as a source of both the methoxy and the methoxycarbonyl groups. This reaction transforms styrene and its derivatives into value‐added β‐methoxy alkanoates and cinnamates, as well as medicinally important five‐membered heterocycles, such as functionalized tetrahydrofurans, γ‐lactones, and pyrrolidines. A ternary β‐diketiminato‐Cu I ‐styrene complex, fully characterized by NMR spectroscopy and X‐ray crystallographic analysis, is capable of catalyzing the same transformation. These findings suggest that pre‐coordination of electron‐rich alkenes to copper might play an important role in accelerating the addition of nucleophilic radicals to electron‐rich alkenes, and could have general implications in the design of novel radical‐based transformations.