3310-66-5Relevant academic research and scientific papers
Aerobically-initiated C(sp3)-H bond amination through the use of activated azodicarboxylates
Ahmed, Nehaal,Chudasama, Vijay,Maruani, Antoine,Shamsabadi, André
, p. 6258 - 6264 (2020)
Significant advancements in C-N bond formation via C-H bond functionalisation have made it a staple in the production of nitrogen-containing compounds in both industry and academia. However, transition metal-free synthesis, particularly in the case of C(sp3)-N formation, has remained a significant challenge to the synthetic community. Herein we report a procedure for α-C(sp3)-H amination of ethereal compounds through use of azodicarboxylates as the nitrogen source and freely-available atmospheric oxygen to access ethereal radical intermediates via aerobic C-H activation. The use of fluorinated alcohols as solvent is observed to greatly increase the efficiency of the reaction and we show experimentally and theoretically the key role of H-bonding between fluorinated alcohols and azodicarboxylates. Calculations of the condensed Fukui functions of a H-bonded fluorinated alcohol-azodicarboxylate complex correlates with a significantly increased susceptibility of azodicarboxylates to undergo reaction with radicals, which informs a number of recent reports in the literature.
Phenylglyoxylic Acid: An Efficient Initiator for the Photochemical Hydrogen Atom Transfer C?H Functionalization of Heterocycles
Papadopoulos, Giorgos N.,Kokotou, Maroula G.,Spiliopoulou, Nikoleta,Nikitas, Nikolaos F.,Voutyritsa, Errika,Tzaras, Dimitrios I.,Kaplaneris, Nikolaos,Kokotos, Christoforos G.
, p. 5934 - 5944 (2020/09/09)
C?H functionalization at the α-position of heterocycles has become a rapidly growing area of research. Herein, a cheap and efficient photochemical method was developed for the C?H functionalization of heterocycles. Phenylglyoxylic acid (PhCOCOOH) could behave as an alternative to metal-based catalysts and organic dyes and provided a very general and wide array of photochemical C?H alkylation, alkenylation, and alkynylation, as well as C?N bond forming reaction methodologies. This novel, mild, and metal-free protocol was successfully employed in the functionalization of a wide range of C?H bonds, utilizing not only O- or N-heterocycles, but also the less studied S-heterocycles.
