5461-49-4Relevant articles and documents
Isomorphism of chiral ammonium salts Ph(All)N+Et(Me)X-·CHCl3
Kostyanovsky, Remir G.,Lyssenko, Konstantin A.,Krutius, Oleg N.,Kostyanovsky, Vasily R.
, p. 19 - 20 (2009)
The title ammonium salts (X = Br, I) were synthesized, the identity of crystal structures for them (space groups P212121, Z = 4) was found, spontaneous resolution of Ph(All)N+Et(Me)Br-·CHCl3 was performed, and the impossibility of replacement of the solvate molecule by CHBr3 or CH2Hal2 (Hal = Cl, Br, I) was demonstrated by 1H NMR and X-ray diffraction studies.
Catalyst-free photoinduced selective oxidative C(sp3)-C(sp3) bond cleavage in arylamines
Duan, Wentao,Lian, Qi,Wang, Songping,Wei, Wentao,Zhou, Jingwei
supporting information, p. 3261 - 3267 (2021/05/21)
Due to the directional nature of sp3-hybridized orbitals and the absence of π-orbitals, the oxidative cleavage of the kinetically and thermodynamically stable C(sp3)-C(sp3) bond is extremely difficult and remains scarcely explored. In this work, under the double argument of quantum mechanics (QM) computations and meticulous experiments on our well-designed C-C single bond cleavage mechanism, we discovered a means of photoinduced selective oxidative C(sp3)-C(sp3) bond cleavage in arylamines, easily achieved by simple visible light irradiation using O2as a benign oxidant under very mild conditions. The utility of our methodology was demonstrated by the C(sp3)-C(sp3) bond cleavage in morpholine/piperazine arylamines with excellent functional group tolerance. Importantly, our methodology is noteworthy, not only in that it does not require any catalysts, but also in that it provides valuable possibilities for the scalable functionalization of clinical drugs and natural products.
Study on the mild, rapid and selective difluorocarbene-mediated triclassification of iododifluoroacetophenone with secondary amines and tree model for product classification
Chen, Xiu-Ping,Han, Jie,Hu, Yin-Jie,Li, Yun-Fang,Wang, Xiang-Cong,Ran, Jian-Xiong,Wang, Zhong-Hua,Wu, Fan-Hong
, (2020/12/14)
Difluorocarbene is a very active and widely used intermediate in organic synthesis. In this work, a room temperature difluorocarbene-mediated triclassification reaction of iododifluoroacetophenone (2) and secondary amines with mild condition, short reaction time (only 10 min) and high selectivity had been studied, which produced one of the following three substances: N-CF2H derivatives (up to 87% yield), formamides (82–89% yield) or the recycled starting secondary amines. This phenomenon was related to the structural stability of the corresponding products. If unstable, it would be hydrolyzed to formamides first, and then further hydrolyzed to starting amines. Based on the geometric structure of the raw materials, the corresponding prediction tree model was established, which provided guidance for the further application of difluoromethylation of Vemurafenib (1ee) and AZD9291 (1ff).
