143998-26-9Relevant articles and documents
Homologation of Electron-Rich Benzyl Bromide Derivatives via Diazo C-C Bond Insertion
Modak, Atanu,Alegre-Requena, Juan V.,De Lescure, Louis,Rynders, Kathryn J.,Paton, Robert S.,Race, Nicholas J.
supporting information, p. 86 - 92 (2021/12/27)
The ability to manipulate C-C bonds for selective chemical transformations is challenging and represents a growing area of research. Here, we report a formal insertion of diazo compounds into the "unactivated"C-C bond of benzyl bromide derivatives catalyzed by a simple Lewis acid. The homologation reaction proceeds via the intermediacy of a phenonium ion, and the products contain benzylic quaternary centers and an alkyl bromide amenable to further derivatization. Computational analysis provides critical insight into the reaction mechanism, in particular the key selectivity-determining step.
Trifluoromethylthiolation and Trifluoromethylselenolation of α-Diazo Esters Catalyzed by Copper
Matheis, Christian,Krause, Thilo,Bragoni, Valentina,Goossen, Lukas J.
supporting information, p. 12270 - 12273 (2016/08/24)
α-Diazo esters are smoothly converted into the corresponding trifluoromethyl thio- or selenoethers by reaction with Me4NSCF3or Me4NSeCF3, respectively, in the presence of catalytic amounts of copper thiocyanate. This straightforward method gives high yields under neutral conditions at room temperature and is applicable to a wide range of functionalized molecules, including diverse α-amino acid derivatives. It is well-suited for the late-stage introduction of trifluoromethylthio or -seleno groups into drug-like molecules.
