19984-39-5Relevant academic research and scientific papers
Visible-Light-Enabled Direct Decarboxylative N-Alkylation
Arman, Hadi D.,Dang, Hang T.,Haug, Graham C.,Larionov, Oleg V.,Nguyen, Viet D.,Nguyen, Vu T.,Vuong, Ngan T. H.
supporting information, p. 7921 - 7927 (2020/04/10)
The development of efficient and selective C?N bond-forming reactions from abundant feedstock chemicals remains a central theme in organic chemistry owing to the key roles of amines in synthesis, drug discovery, and materials science. Herein, we present a dual catalytic system for the N-alkylation of diverse aromatic carbocyclic and heterocyclic amines directly with carboxylic acids, by-passing their preactivation as redox-active esters. The reaction, which is enabled by visible-light-driven, acridine-catalyzed decarboxylation, provides access to N-alkylated secondary and tertiary anilines and N-heterocycles. Additional examples, including double alkylation, the installation of metabolically robust deuterated methyl groups, and tandem ring formation, further demonstrate the potential of the direct decarboxylative alkylation (DDA) reaction.
Mixed er-NHC/phosphine Pd(ii) complexes and their catalytic activity in the Buchwald-Hartwig reaction under solvent-free conditions
Ageshina, Alexandra A.,Sterligov, Grigorii K.,Rzhevskiy, Sergey A.,Topchiy, Maxim A.,Chesnokov, Gleb A.,Gribanov, Pavel S.,Nechaev, Mikhail S.,Asachenko, Andrey F.,Bermeshev, Maxim V.,Melnikova, Elizaveta K.
supporting information, p. 3447 - 3452 (2019/04/30)
A series of novel (NHC)PdCl2-PR3 complexes were synthesized and fully characterized by 1H, 13C, 31P NMR and FT-IR spectroscopy. These complexes showed high catalytic activity toward solvent-free Buchwald-Hartwig amination. Both primary and secondary amines were efficiently utilized under the same reaction conditions. The solvent-free synthesis of valuable N-aryl carbazoles and similar N-heterocyclic systems was described.
A Polystyrene-Cross-Linking Bisphosphine: Controlled Metal Monochelation and Ligand-Enabled First-Row Transition Metal Catalysis
Iwai, Tomohiro,Harada, Tomoya,Shimada, Hajime,Asano, Kiichi,Sawamura, Masaya
, p. 1681 - 1692 (2017/08/15)
A polystyrene-cross-linking bisphosphine PS-DPPBz was synthesized through radical emulsion copolymerization between 4-t-butylstyrene as a monomer and tetravinylated 1,2-bis(diphenylphosphino)benzene (DPPBz) as a 4-fold cross-linker. The location of the DPPBz bisphosphine moiety at the branching points of the cross-linked network organic polymer allowed controlled bisphosphine monochelation to transition metals under conditions where homogeneous ligands may form bischelated single metal complexes or multinuclear complexes. PS-DPPBz showed high ligand performance in first-row transition metal catalysis, enabling challenging molecular transformations that were not possible through the screening of existing homogeneous ligands. In the Ni-catalyzed amination of aryl chlorides with N-alkyl-substituted primary amines, the substrate scope has been expanded to include 2,6-disubstituted aryl chlorides and N-tertiary-alkyl-substituted primary amines. PS-DPPBz was effective for the Ni-catalyzed C-H/C-O coupling between 1,3-azoles and monocyclic aryl pivalates, which showed poor reactivity in the reported homogeneous catalytic system based on 1,2-bis(dicyclohexylphosphino)ethane (DCYPE). The usefulness of the polymer-cross-linking strategy was also demonstrated in alkene hydroboration reactions catalyzed by Cu or Co.
Room-Temperature CuI-Catalyzed Amination of Aryl Iodides and Aryl Bromides
Ding, Xiaomei,Huang, Manna,Yi, Zhou,Du, Dongchen,Zhu, Xinhai,Wan, Yiqian
, p. 5416 - 5423 (2017/05/25)
A general and effective CuI/N′,N′-diaryl-1H-pyrrole-2-carbohydrazide catalyst system was developed for the amination of aryl iodides and bromides at room temperature with good chemoselectivity between -OH and -NH2 groups. Only 5 mol % of CuI and ligands was needed in this protocol to effect the amination of various aryl bromides and aryl iodides with a wide range of aliphatic and aryl amines (1.3 equiv).
Solvent-free and direct C(sp3)-H amination of adamantanes by grinding
Wei, Zhen,Li, Jiarong,Wang, Ning,Zhang, Qi,Shi, Daxin,Sun, Kening
supporting information, p. 1395 - 1400 (2014/02/14)
A facile, direct and environmentally benign conversion of C(sp 3)-H bonds to C(sp3)-N bonds using substoichiometric amount of aprotic superelectrophiles polyhalomethane-AlX3 has been achieved by grinding under solvent-free
Solvolysis-decomposition of N-1-adamantyl-N-p-tolylcarbamoyl chloride in hydroxylic solvents
Kevill, Dennis N.,Upadhyay, Veena
, p. 600 - 606 (2007/10/03)
In hydroxylic solvents, N-1-adamantyl-N-p-tolylcarbamoyl chloride undergoes a facile rate-determing ionization with very little assistance from nucleophilic solvation (very low sensitivity to changes in solvent nucleophilicity). In the relatively nucleophilic aqueous ethanol or aqueous acetone, the cation formed reacts directly with the solvent. In fluoroalcohols, the low nucleophilicity of the solvent allows an effective competition from a pathway involving disproportionation to the 1-adamantyl cation and p-tolyl isocyanate, followed by reaction of the new cation either with solvent or with the chloride ion formed in the initial ionization. Grunwald-Winstein plots against Ycl values show for different binary solvent systems a marked dispersion, which can be considerably reduced by incorporation into the analyses of a term governed by the aromatic ring parameter. (I).
