- Reusable Nickel Nanoparticles-Catalyzed Reductive Amination for Selective Synthesis of Primary Amines
-
The preparation of nickel nanoparticles as efficient reductive amination catalysts by pyrolysis of in situ generated Ni-tartaric acid complex on silica is presented. The resulting stable and reusable Ni-nanocatalyst enables the synthesis of functionalized and structurally diverse primary benzylic, heterocyclic and aliphatic amines starting from inexpensive and readily available carbonyl compounds and ammonia in presence of molecular hydrogen. Applying this Ni-based amination protocol, -NH2 moiety can be introduced in structurally complex compounds, for example, steroid derivatives and pharmaceuticals.
- Murugesan, Kathiravan,Beller, Matthias,Jagadeesh, Rajenahally V.
-
supporting information
p. 5064 - 5068
(2019/03/19)
-
- Reductive amination of ketonic compounds catalyzed by Cp*Ir(III) complexes bearing a picolinamidato ligand
-
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.
- Tanaka, Kouichi,Miki, Takashi,Murata, Kunihiko,Yamaguchi, Ayumi,Kayaki, Yoshihito,Kuwata, Shigeki,Ikariya, Takao,Watanabe, Masahito
-
p. 10962 - 10977
(2019/09/03)
-
- Piperidines from acid-catalysed cyclisations: Pitfalls, solutions and a new ring contraction to pyrrolidines
-
The success of acid-catalysed cyclisations of alka-4-enylamine derivatives to piperidines depends very much on the nature of the amine protecting group: while carbamates and related amides can usually be readily and cleanly transformed, the corresponding sulfonamides react further by ring contraction leading to pyrrolidines, especially when such substrates are sterically crowded.
- Aldmairi, Abdul H.,Griffiths-Jones, Charlotte,Dupauw, Alexis,Henderson, Laura,Knight, David W.
-
p. 3690 - 3694
(2017/09/02)
-
- MOF-derived cobalt nanoparticles catalyze a general synthesis of amines
-
The development of base metal catalysts for the synthesis of pharmaceutically relevant compounds remains an important goal of chemical research. Here, we report that cobalt nanoparticles encapsulated by a graphitic shell are broadly effective reductive amination catalysts. Their convenient and practical preparation entailed template assembly of cobaltdiamine- dicarboxylic acid metal organic frameworks on carbon and subsequent pyrolysis under inert atmosphere.The resulting stable and reusable catalysts were active for synthesis of primary, secondary, tertiary, and N-methylamines (more than 140 examples).The reaction couples easily accessible carbonyl compounds (aldehydes and ketones) with ammonia, amines, or nitro compounds, and molecular hydrogen under industrially viable and scalable conditions, offering cost-effective access to numerous amines, amino acid derivatives, and more complex drug targets.
- Jagadeesh, Rajenahally V.,Murugesan, Kathiravan,Alshammari, Ahmad S.,Neumann, Helfried,Pohl, Marga-Martina,Radnik, J?rg,Beller, Matthias
-
p. 326 - 332
(2017/09/28)
-
- CATALYST COMPOUNDS
-
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.
- -
-
Paragraph 0314; 0322
(2015/03/28)
-
- Primary amines by transfer hydrogenative reductive amination of ketones by using cyclometalated IrIII catalysts
-
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
- Talwar, Dinesh,Salguero, Noemi Poyatos,Robertson, Craig M.,Xiao, Jianliang
-
supporting information
p. 245 - 252
(2014/01/17)
-
- CATALYST COMPOUNDS
-
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.
- -
-
Paragraph 00163; 00171
(2013/11/05)
-
- SUBSTITUTED 4H-IMIDAZO [4, 5, 1-IJ] [1, 6] NAPHTHYRIDINE-9-AMINES AND THEIR PHARMACEUTICAL USE
-
Substituted 4H-imidazo[4,5, 1-ij][1,6]naphthyridine-9-amines of the Formula I : pharmaceutical compositions containing the compounds, intermediates, methods of making the compounds, and methods of use of these compounds as immunomodulators, for inducing cytokine biosynthesis in animals and in the treatment of diseases including viral and neoplastic diseases, are disclosed.
- -
-
Page/Page column 61-62
(2010/11/30)
-
- Thiyl radical mediated racemization of nonactivated aliphatic amines
-
The racemization of nonactivated aliphatic amines has been mediated with alkanethiols and with methyl thioglycolate in the presence of AIBN. The process involves reversible H-abstraction at the chiral center, in a position α relative to nitrogen, by thiyl radical. The knowledge of the reaction enthalpy is critical to select the appropriate thiol. In the absence of experimental values, theoretical calculations of the α-C-H BDEs and the S-H BDE provide a useful guide.
- Escoubet, Stephanie,Gastaldi, Stephane,Vanthuyne, Nicolas,Gil, Gerard,Siri, Didier,Bertrand, Michele P.
-
p. 7288 - 7292
(2007/10/03)
-