6425-43-0Relevant articles and documents
Thiourea-Catalyzed C?F Bond Activation: Amination of Benzylic Fluorides
Houle, Camille,Savoie, Paul R.,Davies, Clotilde,Jardel, Damien,Champagne, Pier Alexandre,Bibal, Brigitte,Paquin, Jean-Fran?ois
, p. 10620 - 10625 (2020/07/24)
We describe the first thiourea-catalyzed C?F bond activation. The use of a thiourea catalyst and Ti(OiPr)4 as a fluoride scavenger allows the amination of benzylic fluorides to proceed in moderate to excellent yields. Preliminary results with S- and O-based nucleophiles are also presented. DFT calculations reveal the importance of hydrogen bonds between the catalyst and the fluorine atom of the substrate to lower the activation energy during the transition state.
Thioglycerol-Stabilized Rhodium Nanoparticles in Biphasic Medium as Catalysts in Multistep Reactions
Guerrero-Ríos, Itzel,Portales-Martínez, Benjamín,Reina, Antonio,Serrano-Maldonado, Alejandro
supporting information, (2020/07/04)
Small rhodium nanoparticles (ca. 3.5 nm) were prepared by the decomposition of an organometallic precursor under hydrogen pressure in glycerol using 1-thioglycerol as stabilizer. Full characterization in the solid state [HR-TEM, EDX, XPS] showed a fcc structure for the Rh0/RhI nanoparticles capped with thiolate ligand. Reduction of different functionalities, including nitro groups and imines, was applied to tandem reductive amination of aldehydes with primary and secondary amines, and to the synthesis of N-substituted anilines from nitrobenzene. In addition, thiolate-capped RhNPs could be recovered and reused up to 5 runs without loss of activity nor selectivity.
Photochemical benzylic bromination in continuous flow using BrCCl3 and its application to telescoped p-methoxybenzyl protection
Otake, Yuma,Williams, Jason D.,Rincón, Juan A.,De Frutos, Oscar,Mateos, Carlos,Kappe, C. Oliver
, p. 1384 - 1388 (2019/02/14)
BrCCl3 represents a rarely used benzylic brominating reagent with complementary reactivity to other reagents. Its reactivity has been revisited in continuous flow, revealing compatibility with electron-rich aromatic substrates. This has brought about the development of a p-methoxybenzyl bromide generator for PMB protection, which was successfully demonstrated on a pharmaceutically relevant intermediate on 11 g scale, giving 91% yield and a PMB-Br space-time-yield of 1.27 kg L?1 h?1