109605-09-6Relevant articles and documents
Visible-Light-Mediated Aerobic Oxidative C(sp3)?C(sp3) Bond Cleavage of Morpholine Derivatives Using 4CzIPN as a Photocatalyst
Dong, Chun-Lin,Huang, Lan-Qian,Guan, Zhi,Huang, Chu-Sheng,He, Yan-Hong
supporting information, p. 3803 - 3811 (2021/06/28)
Herein, a metal-free strategy for the aerobic oxidative cleavage of the inert C(sp3)?C(sp3) bond was developed. Deconstruction of morpholine derivatives was conducted using visible light as an energy source and O2 as an oxidant under mild conditions. This procedure demonstrated suitable selectivity and functional group tolerance. Moreover, a possible mechanism involving a radical process was proposed based on a series of mechanism exploration and control experiments. (Figure presented.).
Catalyst-free photodecarbonylation ofortho-amino benzaldehyde
Li, Lamei,Wang, Songping,Wei, Wentao,Yan, Ming,Zhou, Jingwei
supporting information, p. 3421 - 3426 (2020/06/25)
It is almost a consensus that decarbonylation of the aldehyde group (-CHO) needs to not only be mediated by transition metal catalysts, but also requires severe reaction conditions (high temperature and long reaction time). In this work, inspired by the “conformational-selectivity-based” design strategy, we broke this consensus and discovered a catalyst-free photodecarbonylation of the aldehyde group. It revealed that decarbonylation can be easily achieved with visible light irradiation by introducing a tertiary amine into theortho-position of the aldehyde group. A diverse array of tertiary amines is tolerated by our photodecarbonylation under mild conditions. Furthermore, the (QM) computations of the mechanism and the experiments on well-designed special substrates revealed that our photodecarbonylation depends on the conformational specificity of the aldehyde group and tertiary amine, and occurs through an unusual [1,4]-H shift and a subsequent [1,3]-H shift.
The reaction of primary aromatic amines with alkylene carbonates for the selective synthesis of bis-N-(2-hydroxy)alkylanilines: The catalytic effect of phosphonium-based ionic liquids
Selva, Maurizio,Fabris, Massimo,Lucchini, Vittorio,Perosa, Alvise,Noe, Marco
experimental part, p. 5187 - 5198 (2010/12/25)
At T ≥ 140 °C, different primary aromatic amines (pX-C 6H4NH2; X = H, OCH3, CH3, Cl) react with both ethylene- and propylene-carbonates to yield a chemoselective N-alkylation process: bis-N-(2-hydroxyalkyl)anilines [pX-C 6H4N(CH2CH(R)OH)2; R = H, CH 3] are the major products and the competitive formation of carbamates is substantially ruled out. At 140 °C, under solventless conditions, the model reaction of aniline with ethylene carbonate goes to completion by simply mixing stoichiometric amounts of the reagents. However, a class of phosphonium ionic liquids (PILs) such as tetraalkylphosphonium halides and tosylates turn out to be active organocatalysts for both aniline and other primary aromatic amines. A kinetic analysis monitored by 13C NMR spectroscopy, shows that bromide exchanged PILs are the most efficient systems, able to impart a more than 8-fold acceleration to the reaction. The reactions of propylene carbonate take place at a higher temperature than those of ethylene carbonate, and only in the presence of PIL catalysts. A mechanism based on the Lewis acidity of tetraalkylphosphonium cations and the nucleophilicity of halide anions has been proposed to account for both the reaction chemoselectivity and the function of the catalysts.
