126550-92-3Relevant academic research and scientific papers
Computationally Assisted Mechanistic Investigation into Hypervalent Iodine Catalysis: Cyclization of N-Allylbenzamide
Butt, Smaher E.,Das, Mirdyul,Sotiropoulos, Jean-Marc,Moran, Wesley J.
, p. 15605 - 15613 (2019)
Previous experimental work identified 2-iodoanisole as the best precatalyst for the oxidative cyclization of N-alkenylamides into 2-oxazolines. Herein, we describe our investigation into the effect on the reaction rate based on the structure of the iodoarene precatalyst. We also reveal the mechanism of the cyclization based on DFT modeling and obtain a clear correlation between observed reaction rates and computationally derived activation energies for different iodoarenes. In addition, the rate-limiting step is shown to be the cyclization of the substrate that is zero order in the concentration of the iodoarene precatalyst. The rate of cyclization is found to correlate with the ease of oxidation of the iodoarene; however, the most easily oxidized iodoarenes generate iodine(III) species that decompose readily. Finally, loss of iodoarene from the cyclized intermediate can proceed by either ligand-coupling or SN2 displacement (reductive elimination), and this is shown to be substrate-dependent.
Synthesis of Functionalized Monoaryl-λ3-iodanes through Chemo- and Site-Selective ipso-Substitution Reactions
Komami, Narumi,Matsuoka, Keitaro,Nakano, Ayako,Kojima, Masahiro,Yoshino, Tatsuhiko,Matsunaga, Shigeki
supporting information, p. 1217 - 1220 (2019/01/04)
Monoaryl-λ3-iodanes are potentially attractive arylating agents. They are generally synthesized from aryl iodides via oxidation, which can cause functional group incompatibility, especially when polyfunctionalized derivatives are desired. This work describes the direct synthesis of monoaryl-λ3-iodanes through a chemoselective ipso-substitution reaction of arylgermanes and arylstannanes with iodine tris(trifluoroacetate). The generated iodanes were converted to iodonium ylides or used for further transformations in one pot. The presented method enables the preparation of polyfunctionalized monoaryl-λ3-iodanes.
FLUORINATION OF AROMATIC RING SYSTEMS
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Page/Page column 39, (2010/05/13)
This disclosure relates to reagents and methods useful in the synthesis of aryl fluorides, for example, in the preparation of 18F labeled radiotracers. The reagents and methods provided herein may be used to access a broad range of compounds, including aromatic compounds, heteroaromatic compounds, amino acids, nucleotides, and synthetic compounds.
