1502-03-0Relevant articles and documents
The Synthesis of Primary Amines through Reductive Amination Employing an Iron Catalyst
B?umler, Christoph,Bauer, Christof,Kempe, Rhett
, p. 3110 - 3114 (2020/06/01)
The reductive amination of ketones and aldehydes by ammonia is a highly attractive method for the synthesis of primary amines. The use of catalysts, especially reusable catalysts, based on earth-abundant metals is similarly appealing. Here, the iron-catalyzed synthesis of primary amines through reductive amination was realized. A broad scope and a very good tolerance of functional groups were observed. Ketones, including purely aliphatic ones, aryl–alkyl, dialkyl, and heterocyclic, as well as aldehydes could be converted smoothly into their corresponding primary amines. In addition, the amination of pharmaceuticals, bioactive compounds, and natural products was demonstrated. Many functional groups, such as hydroxy, methoxy, dioxol, sulfonyl, and boronate ester substituents, were tolerated. The catalyst is easy to handle, selective, and reusable and ammonia dissolved in water could be employed as the nitrogen source. The key is the use of a specific Fe complex for the catalyst synthesis and an N-doped SiC material as catalyst support.
Cerium-Catalyzed C-H Functionalizations of Alkanes Utilizing Alcohols as Hydrogen Atom Transfer Agents
An, Qing,Chen, Yuegang,Liu, Weimin,Pan, Hui,Wang, Xin,Wang, Ziyu,Zhang, Kaining,Zuo, Zhiwei
supporting information, p. 6216 - 6226 (2020/04/27)
Modern photoredox catalysis has traditionally relied upon metal-to-ligand charge-transfer (MLCT) excitation of metal polypyridyl complexes for the utilization of light energy for the activation of organic substrates. Here, we demonstrate the catalytic application of ligand-to-metal charge-transfer (LMCT) excitation of cerium alkoxide complexes for the facile activation of alkanes utilizing abundant and inexpensive cerium trichloride as the catalyst. As demonstrated by cerium-catalyzed C-H amination and the alkylation of hydrocarbons, this reaction manifold has enabled the facile use of abundant alcohols as practical and selective hydrogen atom transfer (HAT) agents via the direct access of energetically challenging alkoxy radicals. Furthermore, the LMCT excitation event has been investigated through a series of spectroscopic experiments, revealing a rapid bond homolysis process and an effective production of alkoxy radicals, collectively ruling out the LMCT/homolysis event as the rate-determining step of this C-H functionalization.
Reductive amination of ketonic compounds catalyzed by Cp*Ir(III) complexes bearing a picolinamidato ligand
Tanaka, Kouichi,Miki, Takashi,Murata, Kunihiko,Yamaguchi, Ayumi,Kayaki, Yoshihito,Kuwata, Shigeki,Ikariya, Takao,Watanabe, Masahito
, p. 10962 - 10977 (2019/09/03)
Cp*Ir complexes bearing a 2-picolinamide moiety serve as effective catalysts for the direct reductive amination of ketonic compounds to give primary amines under transfer hydrogenation conditions using ammonium formate as both the nitrogen and hydrogen source. The clean and operationally simple transformation proceeds with a substrate to catalyst molar ratio (S/C) of up to 20,000 at relatively low temperature and exhibits excellent chemoselectivity toward primary amines.
Azetidine derivatives and synthesis method thereof
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Paragraph 0060-0062, (2019/03/26)
The invention belongs to the field of chemical synthesis, and discloses an azetidine derivative and a synthesis method thereof. The structural formula of the target product azetidine derivatives is asshown in formulae (I), (II), (III), (IV) and (V). The compounds of the formulae are compounds containing an azetidine skeleton, and a nitrogen atom in the skeleton is protected by 2-picolinic acid. The target product azetidine derivatives can be: azetidinyl amide derivatives, azabicyclo[x.1.1] amide derivatives (x=3, 4, 5, 6, 7, 8, 9), azabicyclo[4.1.1] amide derivatives having a substituent at the ring, azabicyclo[4.2.0] amide derivatives and azetidine derivatives containing spirocyclic quaternary carbon. The azetidine derivatives of the present invention have certain protective effect on hydrogen peroxide-induced oxidative stress damage of HC cells.
Polycyclic Azetidines and Pyrrolidines via Palladium-Catalyzed Intramolecular Amination of Unactivated C(sp3)-H Bonds
Zhao, Jie,Zhao, Xiao-Jing,Cao, Pei,Liu, Ji-Kai,Wu, Bin
supporting information, p. 4880 - 4883 (2017/09/23)
A novel strategy to construct complex polycyclic nitrogen-containing heterocycles from aliphatic amines via picolinamide-assisted palladium-catalyzed C-H bond activation reaction was reported. The reaction exhibits broad substrate scope for the synthesis of various azabicyclic scaffolds, including azetidines and tropane-class alkaloids. Application of this method to naturally occurring (-)-cis-myrtanylamine, an unprecedented type of carbon-carbon bond activation, in which the electron-pair involved initiates an intramolecular "SN2-like" displacement of a cyclopalladium-fragment from a tertiary center, is described.
Synthesis of Aliphatic Azides by Photoinduced C(sp3)-H Azidation
Kamijo, Shin,Watanabe, Mizuki,Kamijo, Kaori,Tao, Keisuke,Murafuji, Toshihiro
, p. 115 - 121 (2015/12/26)
A photoinduced synthesis of aliphatic azides was achieved in a single step starting from the parent cyclic alkanes, as well as from tetrahydrofuran and pyrrolidine derivatives. The reaction proceeds via direct azidation of C(sp3)-H bonds in the presence of 4-benzoylpyridine under photoirradiation conditions utilizing tosyl azide as the azide source. The chemoselective C-H mono-azidation at room temperature and the formation of azide compounds in spite of their potential photolability are the key features of the present transformation.
CATALYST COMPOUNDS
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Paragraph 0314; 0322, (2015/03/28)
The present invention relates to an iridium-based catalyst compound for hydrogenating reducible moieties, especially imines and iminiums, the catalyst compounds being defined by the formulas: where ring B is either itself polycyclic, or ring B together with R is polycyclic. The catalysts of the invention are particularly effective in reductive amination procedures 10 which involve the in situ generation of the imine or iminium under reductive hydrogenative conditions.
Selective synthesis of primary amines by reductive amination of ketones with ammonia over supported Pt catalysts
Nakamura, Yoichi,Kon, Kenichi,Touchy, Abeda Sultana,Shimizu, Ken-Ichi,Ueda, Wataru
, p. 921 - 924 (2015/03/18)
Supported platinum catalysts are studied for the reductive amination of ketones under ammonia and hydrogen. For a model reaction with 2-adamantanone, Pt-loaded MoOx/TiO2 (Pt-MoOx/TiO2) shows the highest yield of primary amine. The catalyst is effective for the selective transformation of various aliphatic and aromatic ketones to the corresponding primary amines, which demonstrates the first example of the selective synthesis of primary amines by this reaction. The yield of the amine increases with increase in the negative shift of the C￡O stretching band in the infrared spectra of adsorbed acetone on the catalysts, suggesting that Lewis acid sites on the support material play an important role in this catalytic system.
Primary amines by transfer hydrogenative reductive amination of ketones by using cyclometalated IrIII catalysts
Talwar, Dinesh,Salguero, Noemi Poyatos,Robertson, Craig M.,Xiao, Jianliang
supporting information, p. 245 - 252 (2014/01/17)
Cyclometalated iridium complexes are found to be versatile catalysts for the direct reductive amination (DRA) of carbonyls to give primary amines under transfer-hydrogenation conditions with ammonium formate as both the nitrogen and hydrogen source. These complexes are easy to synthesise and their ligands can be easily tuned. The activity and chemoselectivity of the catalyst towards primary amines is excellent, with a substrate to catalyst ratio (S/C) of 1000 being feasible. Both aromatic and aliphatic primary amines were obtained in high yields. Moreover, a first example of homogeneously catalysed transfer-hydrogenative DRA has been realised for β-keto ethers, leading to the corresponding β-amino ethers. In addition, non-natural α-amino acids could also be obtained in excellent yields with this method. Reduce the work! A broad range of ketones have been successfully aminated to afford primary amines under transfer-hydrogenation conditions by using ammonium formate as the amine source and 0.1 mol % of a cyclometalated IrIII catalyst (see scheme). Copyright
N-alkylation of ammonia and amines with alcohols catalyzed by Ni-loaded CaSiO3
Shimizu, Ken-Ichi,Kanno, Shota,Kon, Kenichi,Hakim Siddiki,Tanaka, Hideyuki,Sakata, Yoshihisa
, p. 134 - 138 (2014/06/09)
Nickel nanoparticles loaded onto calcium silicate (Ni/CaSiO3) have been prepared by ion-exchange method followed by in situ H 2-reduction of the calcined precursor. Ni/CaSiO3 was found to be effective for the catalytic direct synthesis of primary amines from alcohols and NH3 under relatively mild conditions. Various aliphatic alcohols are tolerated, and the turnover number (TON) was higher than those of Ru-based homogeneous catalysts. The catalyst was recoverable and was reused. Effects of the surface oxidation states and particle size of Ni on the catalytic activity were studied by infrared (IR) investigation of the states of adsorbed CO and transmission electron microscopy (TEM). It is clarified that the surface Ni0 sites on small (3 nm) sized Ni nanoparticles are the catalytically active species. Ni/CaSiO3 was also effective for the alkylation of anilines and aliphatic amines with various alcohols (benzyl and aliphatic alcohols) under additive free conditions; primary amines were converted into secondary amines and secondary amines into tertiary amines.
