123570-21-8Relevant articles and documents
Base-Directed Photoredox Activation of C-H Bonds by PCET
Ener, Maraia E.,Darcy, Julia W.,Menges, Fabian S.,Mayer, James M.
, p. 7175 - 7180 (2020)
Photoredox catalysis using proton-coupled electron transfer (PCET) has emerged as a powerful method for bond transformations. We previously employed traditional chemical oxidants to achieve multiple-site concerted proton-electron transfer (MS-CPET) activation of a C-H bond in a proof-of-concept fluorenyl-benzoate substrate. As described here, photoredox oxidation of the fluorenyl-benzoate follows the same rate constant vs driving force trend determined for thermal MS-CPET. Analogous photoredox catalysis enables C-H activation and H/D exchange in a number of additional substrates with favorably positioned bases. Mechanistic studies support our hypothesis that MS-CPET is a viable pathway for bond activation for substrates in which the C-H bond is weak, while stepwise carboxylate oxidation and hydrogen atom transfer likely predominate for stronger C-H bonds.
Two-chamber hydrogen generation and application: Access to pressurized deuterium gas
Modvig, Amalie,Andersen, Thomas L.,Taaning, Rolf H.,Lindhardt, Anders T.,Skrydstrup, Troels
, p. 5861 - 5868 (2014/07/08)
Hydrogen and deuterium gas were produced and directly applied in a two-chamber system. These gaseous reagents were generated by the simple reaction of metallic zinc with HCl in water for H2 and DCl in deuterated water for D2. The setup proved efficient in classical Pd-catalyzed reductions of ketones, alkynes, alkenes, etc. in near-quantitative yields. The method was extended to the synthesis and isotope labeling of quinoline and 1,2,3,4-tetrahydroquinoline derivatives. Finally, CX-546 and Olaparib underwent efficient Ir-catalyzed hydrogen isotope exchange reactions.
