294209-40-8Relevant articles and documents
Redox Self-Adaptation of a Nitrene Transfer Catalyst to the Substrate Needs
Gouré, Eric,Senthilnathan, Dhurairajan,Coin, Guillaume,Albrieux, Florian,Avenier, Frédéric,Dubourdeaux, Patrick,Lebrun, Colette,Maldivi, Pascale,Latour, Jean-Marc
, p. 4305 - 4309 (2017)
The development of iron catalysts for carbon–heteroatom bond formation, which has attracted strong interest in the context of green chemistry and nitrene transfer, has emerged as the most promising way to versatile amine synthetic processes. A diiron system was previously developed that proved efficient in catalytic sulfimidations and aziridinations thanks to an FeIIIFeIV active species. To deal with more demanding benzylic and aliphatic substrates, the catalyst was found to activate itself to a FeIIIFeIVL. active species able to catalyze aliphatic amination. Extensive DFT calculations show that this activation event drastically enhances the electron affinity of the active species to match the substrates requirements. Overall this process consists in a redox self-adaptation of the catalyst to the substrate needs.
Organophotoredox-Catalyzed Decarboxylative N-Alkylation of Sulfonamides
Nakagawa, Masanari,Nagao, Kazunori,Ikeda, Zenichi,Reynolds, Matthew,Ibá?ez, Ignacio,Wang, Junsi,Tokunaga, Norihito,Sasaki, Yusuke,Ohmiya, Hirohisa
, p. 3930 - 3933 (2021/08/03)
We developed an organophotoredox-catalyzed reaction for N-alkylation of sulfonamides with aliphatic carboxylic acid-derived redox active esters as alkylating reagents. Under mild and transition metal-free conditions, a series of functionalized N-alkylated sulfonamides were prepared. This protocol also enabled the functionalization of pharmaceutical drugs bearing a sulfonamide or carboxylic acid moiety. This radical-mediated process allowed the assembly of three components including sulfonamides, redox active esters, and alkenes to yield complex sulfonamides in a one-pot manner.
Observation of a Photogenerated Rh2 Nitrenoid Intermediate in C-H Amination
Das, Anuvab,Maher, Andrew G.,Telser, Joshua,Powers, David C.
supporting information, p. 10412 - 10415 (2018/08/28)
Rh2-catalyzed C-H amination is a powerful method for nitrogenating organic molecules. While Rh2 nitrenoids are often invoked as reactive intermediates in these reactions, the exquisite reactivity and fleeting lifetime of these species has precluded their observation. Here, we report the photogeneration of a transient Rh2 nitrenoid that participates in C-H amination. The developed approach to Rh2 nitrenoids, based on photochemical cleavage of N-Cl bonds in N-chloroamido ligands, has enabled characterization of a reactive Rh2 nitrenoid by mass spectrometry and transient absorption spectroscopy. We anticipate that photogeneration of metal nitrenoids will contribute to the development of C-H amination catalysis by providing tools to directly study the structures of these critical intermediates.
