73747-25-8Relevant articles and documents
Minimization of Back-Electron Transfer Enables the Elusive sp3 C?H Functionalization of Secondary Anilines
Zhao, Huaibo,Leonori, Daniele
supporting information, p. 7669 - 7674 (2021/03/08)
Anilines are some of the most used class of substrates for application in photoinduced electron transfer. N,N-Dialkyl-derivatives enable radical generation α to the N-atom by oxidation followed by deprotonation. This approach is however elusive to monosubstituted anilines owing to fast back-electron transfer (BET). Here we demonstrate that BET can be minimised by using photoredox catalysis in the presence of an exogenous alkylamine. This approach synergistically aids aniline SET oxidation and then accelerates the following deprotonation. In this way, the generation of α-anilinoalkyl radicals is now possible and these species can be used in a general sense to achieve divergent sp3 C?H functionalization.
Copper-Catalyzed Cyanoalkylation of Amines via C-C Bond Cleavage: An Approach for C(sp3)-N Bond Formations
Yang, Lin,Zhang, Jia-Yu,Duan, Xin-Hua,Gao, Pin,Jiao, Jiao,Guo, Li-Na
, p. 8615 - 8629 (2019/08/30)
The efficient copper-catalyzed cyanoalkylation of amines via C-C bond cleavage has been demonstrated. Distinctive features of this procedure involves mild conditions, broad range of nitrogen nucleophiles, high selectivity, and good functional group tolerance, thus providing a useful approach for the C(sp3)-N bond formations. Most importantly, this protocol is applicable to the late-stage functionalization of natural products, amino acid esters, and drugs. Mechanistic studies suggest that a radical intermediate was involved in this transformation.
Single-Electron-Transfer-Induced C(sp3)-N Couplings via C-C Bond Cleavage of Cycloketoxime Esters
Shi, Zhuangzhi,Wang, Minyan,Zhao, Binlin
, (2019/08/26)
A practical single-electron-transfer-induced selective C(sp3)-N coupling of cycloketoximes with anilines via C-C bond cleavage under copper-catalytic and synergetic photoredox/copper-catalytic reaction systems has been uncovered. These two powerful and simple protocols demonstrated excellent selectivity and good functional group compatibility without any base or ligand control. Preliminary mechanistic experiments indicated that a radical-mediated process was involved in these transformations.
Copper-catalyzed ring-opening C(sp3)-N coupling of cycloketone oxime esters: Access to 1°, 2° and 3° alkyl amines
Tian, Li,Gao, Shuangqiu,Wang, Rui,Li, Yang,Tang, Chunlin,Shi, Lili,Fu, Junkai
supporting information, p. 5347 - 5350 (2019/05/10)
A novel copper-catalyzed C(sp3)-N coupling of cycloketone oxime esters with nitrogen nucleophiles has been realized. All of the N-aryl/alkylanilines, anilines and benzophenone imine could be employed in this protocol to produce a variety of 1°, 2° and 3° alkyl amines in one or two steps. These resultant cyano-containing alkyl amines were proven to be versatile synthetic building blocks in a variety of chemical transformations.
Microwave-assisted cyclizations promoted by polyphosphoric acid esters: A general method for 1-aryl-2-iminoazacycloalkanes
Díaz, Jimena E.,Mollo, María C.,Orelli, Liliana R.
supporting information, p. 2026 - 2031 (2016/10/05)
The first general procedure for the synthesis of 5 to 7-membered 1-aryl-2-iminoazacycloalkanes is presented, by microwave-assisted ring closure of ω-arylaminonitriles promoted by polyphosphoric acid (PPA) esters. 1-Aryl-2-iminopyrrolidines were easily pre
Room temperature solvent free aza-Michael reactions over nano-cage mesoporous materials
Kalita, Pranjal,Pegu, Choitayna Dev,Dutta, Prantu,Baruah, Pranjal K.
, p. 145 - 150 (2014/08/18)
An efficient highly acidic three dimensional mesoporous aluminosilicate nano-cage material Al-KIT5, exhibited excellent catalytic activity in solvent free room temperature aza-Michael reactions of amines with α,β- unsaturated carbonyl compounds to produce β-amino carbonyl compounds with 100% product selectivity in a short reaction time. The high acidity, 3D pores, and a huge space in the nano-cages materials make them attractive candidate for carrying out important organic reactions. The catalyst provide a simple, easy to handle method, and could be used to solve the problems of corrosion, toxicity, waste production, and a high cost that are being currently encountered by the conventional homogeneous catalysts.
Synthesis of 1,6-disubstituted 4,5,6,7-tetrahydropyrazolo[3,4-c]pyridin-7- one derivatives and evaluation of their anticancer activity
Devegowda, Vani Nelamane,Seo, Seon Hee,Pae, Ae Nim,Nam, Ghilsoo,Choi, Kyung Il
scheme or table, p. 647 - 650 (2012/05/04)
Promising anticancer compounds of the type 1,6-disubstituted 4,5,6,7-tetrahydropyrazolo[3,4-c]pyridin-7-ones were identified. The target compounds were readily synthesized in a large scale via a sequence of reactions starting from the commercially available primary amines. Their in vitro anti-proliferative activity has been evaluated on prostate (DU-145), colon (HT-29 and HCT-116) and melanoma (A375P) human cancer cell lines. The relationships between the structure and the anticancer activity, covering all tested cancer cell lines, revealed that the compound 5c with 2,4-dimethylphenyl substituent at R2 was the most potent with the IC50 values in the range as low as 0.16 to 0.40 μM.
Selective N-alkylation of amines using nitriles under hydrogenation conditions: Facile synthesis of secondary and tertiary amines
Ikawa, Takashi,Fujita, Yuki,Mizusaki, Tomoteru,Betsuin, Sae,Takamatsu, Haruki,Maegawa, Tomohiro,Monguchi, Yasunari,Sajiki, Hironao
, p. 293 - 304 (2012/02/01)
Nitriles were found to be highly effective alkylating reagents for the selective N-alkylation of amines under catalytic hydrogenation conditions. For the aromatic primary amines, the corresponding secondary amines were selectively obtained under Pd/C-catalyzed hydrogenation conditions. Although the use of electron poor aromatic amines or bulky nitriles showed a lower reactivity toward the reductive alkylation, the addition of NH4OAc enhanced the reactivity to give secondary aromatic amines in good to excellent yields. Under the same reaction conditions, aromatic nitro compounds instead of the aromatic primary amines could be directly transformed into secondary amines via a domino reaction involving the one-pot hydrogenation of the nitro group and the reductive alkylation of the amines. While aliphatic amines were effectively converted to the corresponding tertiary amines under Pd/C-catalyzed conditions, Rh/C was a highly effective catalyst for the N-monoalkylation of aliphatic primary amines without over-alkylation to the tertiary amines. Furthermore, the combination of the Rh/C-catalyzed N-monoalkylation of the aliphatic primary amines and additional Pd/C-catalyzed alkylation of the resulting secondary aliphatic amines could selectively prepare aliphatic tertiary amines possessing three different alkyl groups. According to the mechanistic studies, it seems reasonable to conclude that nitriles were reduced to aldimines before the nucleophilic attack of the amine during the first step of the reaction.
An efficient synthesis of N-arylputrescines and cadaverines
Link, Natalia P.,Díaz, Jimena E.,Orelli, Liliana R.
scheme or table, p. 751 - 754 (2009/07/18)
We present a two-step, general synthesis of N-aryl-putrescines and cadaverines, by cesium carbonate mediated alkylation of anilines with ω-chloronitriles and subsequent reduction. The cesium-mediated alkylation shows remarkable selectivity towards the mon
