64728-42-3Relevant academic research and scientific papers
Selective Functionalization of Hydrocarbons Using a ppm Bioinspired Molecular Tweezer via Proton-Coupled Electron Transfer
Chen, Hongyu,Wang, Lingling,Xu, Sheng,Liu, Xiaohui,He, Qian,Song, Lijuan,Ji, Hongbing
, p. 6810 - 6815 (2021/06/28)
An expanded porphyrin-biscopper hexaphyrin was introduced as a bioinspired molecular tweezer to co-catalyze functionalization of C(sp3)-H bonds. Theoretical and experimental investigations suggested that the biscopper hexaphyrin served as a molecular tweezer to mimic the enzymatic orientation/proximity effect, efficiently activating the N-hydroxyphthalimide (NHPI) via light-free proton-coupled electron transfer (PCET), at an exceptionally low catalyst loading of 10 mol ppm. The resulting N-oxyl radical (PINO) was versatile for chemoselective C-H oxidation and amination of hydrocarbons.
Radical amination of C(sp3)-H bonds using N -hydroxyphthalimide and dialkyl azodicarboxylate
Amaoka, Yuuki,Kamijo, Shin,Hoshikawa, Tamaki,Inoue, Masayuki
, p. 9959 - 9969 (2013/01/15)
A direct conversion of C(sp3)-H bonds to C(sp3)-N bonds has been achieved by utilizing catalytic N-hydroxyphthalimide (NHPI) and stoichiometric dialkyl azodicarboxylate. NHPI functions as a precursor of the electron-deficient phthalimide N-oxyl radical (PINO) to abstract hydrogens, and dialkyl azodicarboxylate acts as a trapping agent of the resultant carbon radical to generate the hydrazine derivatives. This C-H amination proceeds in a highly chemoselective manner with a wide applicability to functionalize benzylic, propargylic, and aliphatic C-H bonds. Furthermore, the obtained hydrazine compounds were readily converted to the corresponding carbamates or amines. Hence, the present protocol for direct introduction of the nitrogen functionality serves as a powerful tool for efficient construction of nitrogen-substituted natural products and pharmaceuticals.
Ene Reactions of Conjugated Dienes. 2. Dependence of Rate on Degree of Hydrogen Removed and s-Cis or s-Trans Diene Character
Jacobson, Barry M.,Arvanitis, Georgia M.,Eliasen, Carol A.,Mitelman, Rimma
, p. 194 - 201 (2007/10/02)
The rates of the ene reactions between diethyl diazenedicarboxylate and a number of dienes have been measured and product structures determined.Accelerated reactions are observed with 1,3-cyclohexadienes but not with dienes held fixed in the s-trans form.Within the first set of systems tertiary hydrogens are much more reactive than secondary.Within the second set secondary are (in turn) more reactive than primary.There is no apparent correlation between the rate of the Diels-Alder reaction of the 1,3-cyclohexadienes with maleic anhydride and the rate of ene reaction with the diazenedicarboxylate.
