614-30-2Relevant academic research and scientific papers
Iridium/graphene nanostructured catalyst for the: N -alkylation of amines to synthesize nitrogen-containing derivatives and heterocyclic compounds in a green process
Chen, Tsun-Ren,Chen, Yi-Sheng,Chen, Yu-Tung,Lee, Wen-Jen,Lin, Yen-Hsing,Wang, Hao-Chen
, p. 4760 - 4770 (2022/02/21)
A facile iridium/graphene-catalyzed methodology providing an efficient synthetic route for C-N bond formation is reported. This catalyst can directly promote the formation of C-N bonds, without pre-activation steps, and without solvents, alkalis and other additives. This protocol provides a direct N-alkylation of amines using a variety of primary and secondary alcohols with good selectivity and excellent yields. Charmingly, the use of diols resulted in intermolecular cyclization of amines, and such products are privileged structures in biologically active compounds. Two examples illustrate the advantages of this catalyst in organic synthesis: the tandem catalysis to synthesize hydroxyzine, and the intermolecular cyclization to synthesize cyclizine. Water is the only by-product, which makes this catalytic process sustainable and environmentally friendly. This journal is
Hydroborative reduction of amides to amines mediated by La(CH2C6H4NMe2-: O)3
Gong, Mingliang,Guo, Chenjun,Luo, Yunjie,Xie, Hongzhen,Zhang, Fangcao
, p. 779 - 791 (2022/01/22)
The deoxygenative reduction of amides to amines is a great challenge for resonance-stabilized carboxamide moieties, although this synthetic strategy is an attractive approach to access the corresponding amines. La(CH2C6H4NMe2-o)3, a simple and easily accessible lanthanide complex, was found to be highly efficient not only for secondary and tertiary amide reduction, but also for the most challenging primary reduction with pinacolborane. This protocol exhibited good tolerance for many functional groups and heteroatoms, and could be applied to gram-scale synthesis. The active species in this catalytic cycle was likely a lanthanide hydride.
Synthesis of N-heterocyclic carbene-Pd(II)-5-phenyloxazole complexes and initial studies of their catalytic activity toward the Buchwald-Hartwig amination of aryl chlorides
Zhang, Zhi-Mao,Xu, Yu-Ting,Shao, Li-Xiong
, (2021/04/19)
Three new N-heterocyclic carbene (NHC)-Pd(II) complexes using 5-phenyloxazole as the ancillary ligand have been obtained in moderate to good yields by a one-pot reaction of the corresponding imidazolium salts, palladium chloride and 5-phenyloxazole under mild conditions. Initial studies showed that one of the complexes is an efficient catalyst for the Buchwald-Hartwig amination of aryl chlorides with various secondary and primary amines under the varied catalyst loading of 0.01-0.05 mol%, thus it will enrich the chemistry of NHCs and give an alternative catalyst for the coupling of challenging while cost-low aryl chlorides.
BF3·Et2O as a metal-free catalyst for direct reductive amination of aldehydes with amines using formic acid as a reductant
Fan, Qing-Hua,Liu, Xintong,Luo, Zhenli,Pan, Yixiao,Xu, Lijin,Yang, Ji,Yao, Zhen,Zhang, Xin
supporting information, p. 5205 - 5211 (2021/07/29)
A versatile metal- and base-free direct reductive amination of aldehydes with amines using formic acid as a reductant under the catalysis of inexpensive BF3·Et2O has been developed. A wide range of primary and secondary amines and diversely substituted aldehydes are compatible with this transformation, allowing facile access to various secondary and tertiary amines in high yields with wide functional group tolerance. Moreover, the method is convenient for the late-stage functionalization of bioactive compounds and preparation of commercialized drug molecules and biologically relevant N-heterocycles. The procedure has the advantages of simple operation and workup and easy scale-up, and does not require dry conditions, an inert atmosphere or a water scavenger. Mechanistic studies reveal the involvement of imine activation by BF3and hydride transfer from formic acid.
Reductive amination of ketones/aldehydes with amines using BH3N(C2H5)3as a reductant
Zou, Qizhuang,Liu, Fei,Zhao, Tianxiang,Hu, Xingbang
supporting information, p. 8588 - 8591 (2021/09/04)
Herein, we report the first example of efficient reductive amination of ketones/aldehydes with amines using BH3N(C2H5)3 as a catalyst and a reductant under mild conditions, affording various tertiary and secondary amines in excellent yields. A mechanistic study indicates that BH3N(C2H5)3 plays a dual function role of promoting imine and iminium formation and serving as a reductant in reductive amination. This journal is
Visible-Light-Driven Stereoselective Annulation of Alkyl Anilines and Dibenzoylethylenes via Electron Donor-Acceptor Complexes
Runemark, August,Zacharias, Savannah C.,Sundén, Henrik
, p. 1901 - 1910 (2021/02/05)
A catalyst-free, stereoselective visible-light-driven annulation reaction between alkenes and N,N-substituted dialkyl anilines for the synthesis of substituted tetrahydroquinolines is presented. The reaction is driven by the photoexcitation of an electron donor-acceptor (EDA) complex, and the resulting products are obtained in good to high yields with complete diastereoselectivity. Mechanistic rationale and photochemical characterization of the EDA-complex are provided.
Dirhodium-Catalyzed Chemo-and Site-Selective C-H Amidation of N, N-Dialkylanilines
Chen, Gong,Arai, Kenta,Morisaki, Kazuhiro,Kawabata, Takeo,Ueda, Yoshihiro
supporting information, p. 728 - 732 (2021/01/18)
A method for dirhodium-catalyzed C(sp 3)-H amidation of N, N-dimethylanilines was developed. Chemoselective C(sp 3)-H amidation of N-methyl group proceeded exclusively in the presence of C(sp 2)-H bonds of the electron-rich aromatic ring. Site-selective C(sp 3)-H amidation proceeded exclusively at the N-methyl group of N-methyl-N-Alkylaniline derivatives with secondary, tertiary, and benzylic C(sp 3)-H bonds α to a nitrogen atom.
Visible light-induced N-methyl activation of unsymmetric tertiary amines
Perumal, Gopi,Kandasamy, Mohanraj,Ganesan, Balaji,Govindan, Karthick,Sathya, Harsha,Hung, Min-Yuan,Chandru Senadi, Gopal,Wu, Ya-Ching,Lin, Wei-Yu
supporting information, (2021/01/09)
In the presence of methylene group, selective N-methyl activation of tertiary amines has been accomplished with the aid of visible light using organic photocatalyst under air. This protocol explores numerous aliphatic and aromatic substituted tetra-hydroquinoline analogues from various tertiary amines and maleimides. Furthermore, this approach was applied to activate the methyl group of N-methyl carbazole to generate the biologically active molecule.
A Photocatalytic Regioselective Direct Hydroaminoalkylation of Aryl-Substituted Alkenes with Amines
Larionova, Natalia A.,Ondozabal, Jun Miyatake,Smith, Emily G.,Cambeiro, Xacobe C.
supporting information, p. 5383 - 5388 (2021/07/26)
A photocatalytic method for the α-selective hydroaminoalkylation of cinnamate esters has been developed. The reaction involves the regioselective addition of α-aminoalkyl radicals generated from aniline derivatives or aliphatic amines to the α-position of unsaturated esters. The scope of aromatic alkenes was extended to styrenes undergoing hydroaminoalkylation with anti-Markovnikov selectivity, which confirms the importance of the aromatic group at the β-position. Simple scale-up is demonstrated under continuous flow conditions, highlighting the practicality of the method.
Visible-Light-Induced C(sp2)-C(sp3) Cross-Dehydrogenative-Coupling Reaction of N-Heterocycles with N-Alkyl- N-methylanilines under Mild Conditions
Zhang, Hong-Yu,Chen, Jianjun,Lu, Cong-Cong,Han, Ya-Ping,Zhang, Yuecheng,Zhao, Jiquan
, p. 11723 - 11735 (2021/09/02)
Disclosed herein is a cross-dehydrogenative-coupling reaction of N-heterocycles including 1,2,4-triazine-3,5(2H, 4H)-diones and quinoxaline-2(1H)-ones with N-methylanilines to form C(sp2)-C(sp3) under visible-light illumination and ambient air at room temperature. In this process, easily available Ru(bpy)3Cl2·6H2O serves as the catalyst, and air acts as the green oxidant. This method features high atom economy, environmental friendliness, and convenient operation and provides an efficient and practical access to aminomethyl-substituted N-heterocycles with extensive functional group compatibility in 40-86% yields.
