17061-63-1Relevant academic research and scientific papers
Selective aerobic oxidation of methanol in the coexistence of amines by nanoporous gold catalysts: Highly efficient synthesis of formamides
Tanaka, Shinya,Minato, Taketoshi,Ito, Eisuke,Hara, Masahiko,Kim, Yousoo,Yamamoto, Yoshinori,Asao, Naoki
, p. 11832 - 11836 (2013)
Holey gold: Highly selective aerobic oxidation of methanol over alkylamines was achieved with a reusable nanoporous gold (AuNPore) catalyst that was fabricated from a Au-Ag alloy (see figure). This excellent chemoselectivity enabled direct N-formylation of alkylamines from a mixture of methanol and amines. The remarkable catalytic activity was attributed to the synergistic effect between gold and the residual silver remaining in the AuNPore. Copyright
Manganese-Catalyzed N-Formylation of Amines by Methanol Liberating H2: A Catalytic and Mechanistic Study
Chakraborty, Subrata,Gellrich, Urs,Diskin-Posner, Yael,Leitus, Gregory,Avram, Liat,Milstein, David
, p. 4229 - 4233 (2017)
The first example of a base metal (manganese) catalyzed acceptorless dehydrogenative coupling of methanol and amines to form formamides is reported herein. The novel pincer complex (iPr-PNHP)Mn(H)(CO)2 catalyzes the reaction under mild conditions in the absence of any additives, bases, or hydrogen acceptors. Mechanistic insight based on the observation of an intermediate and DFT calculations is also provided.
ZIF-67 Derived Co/NC Nanoparticles Enable Catalytic Leuckart-type Reductive Amination of Bio-based Carbonyls to N-Formyl Compounds
Li, Chuanhui,Meng, Ye,Yang, Song,Li, Hu
, p. 5166 - 5177 (2021/10/25)
It is of great significance to develop non-precious metal catalysts with excellent catalytic activity, stability, and acid resistance for biomass valorization. Herein, catalytic amination of biomass carbonyl compounds was achieved via a Leuckart-type reaction over Co nanoparticles (NPs) embedded N-doped carbon catalyst, which was prepared by thermolysis of ZIF-67 precursor at different temperatures in the N2 atmosphere. The Co/NC-800 catalyst exhibited excellent catalytic activity and recyclability in furfural reductive amination to mono-substituted formamide, which was attributed to the synergistic catalytic action of Co NPs and nitrogen base sites of the catalyst. The reductive amination mechanisms were elucidated by theoretical calculations, and showed that the initial formation of C?N bond was derived from the condensation of furfural and formamide, followed by dehydration to form C=N double bond, which was then reduced by hydrogen species Co?H? and NH+. The developed catalytic system was applicable to different carbonyls for the synthesis of corresponding N-formyl compounds with up to 99 % yield.
(o-Phenylenediamino)borylstannanes: Efficient Reagents for Borylation of Various Alkyl Radical Precursors
Suzuki, Kensuke,Nishimoto, Yoshihiro,Yasuda, Makoto
supporting information, p. 3968 - 3973 (2020/12/30)
(o-Phenylenediamino)borylstannanes were newly synthesized to achieve radical boryl substitutions of a variety of alkyl radical precursors. Dehalogenative, deaminative, decharcogenative, and decarboxylative borylations proceeded in the presence of a radica
Chromium-catalysed efficient: N -formylation of amines with a recyclable polyoxometalate-supported green catalyst
Dan, Demin,Chen, Fubo,Zhao, Whenshu,Yu, Han,Han, Sheng,Wei, Yongge
supporting information, p. 90 - 94 (2021/01/11)
A simple and efficient protocol for the formylation of amines with formic acid, catalyzed by a polyoxometalate-based chromium catalyst, is described. Notably, this method shows excellent activity and chemoselectivity for the formylation of primary amines; diamines have also been successfully employed. Importantly, the chromium catalyst is potentially non-toxic, environmentally benign and safer than the widely used high valence chromium catalysts such as CrO3 and K2Cr2O7. The catalyst can be recycled several times with a negligible impact on activity. Finally, a plausible mechanism is provided based on the observation of intermediate and control experiments.
Tetracoordinate borates as catalysts for reductive formylation of amines with carbon dioxide
Du, Chen-Xia,Huang, Zijun,Jiang, Xiaolin,Li, Yuehui,Makha, Mohamed,Wang, Fang,Zhao, Dongmei
supporting information, p. 5317 - 5324 (2020/09/17)
We report sodium trihydroxyaryl borates as the first robust tetracoordinate organoboron catalysts for reductive functionalization of CO2. These catalysts, easily synthesized from condensing boronic acids with metal hydroxides, activate main group element-hydrogen (E-H) bonds efficiently. In contrast to BX3 type boranes, boronic acids and metal-BAr4 salts, under transition metal-free conditions, sodium trihydroxyaryl borates exhibit high reactivity of reductive N-formylation toward a variety of amines (106 examples), including those with functional groups such as ester, olefin, hydroxyl, cyano, nitro, halogen, MeS-, ether groups, etc. The over-performance to catalyze formylation of challenging pyridyl amines affords a promising alternative method to the use of traditional formylation reagents. Mechanistic investigation supports electrostatic interactions as the key for Si/B-H activation, enabling alkali metal borates as versatile catalysts for hydroborylation, hydrosilylation, and reductive formylation/methylation of CO2.
Scope and limitations of reductive amination catalyzed by half-sandwich iridium complexes under mild reaction conditions
Nguyen, Dat P.,Sladek, Rudolph N.,Do, Loi H.
supporting information, (2020/07/15)
The conversion of aldehydes and ketones to 1° amines could be promoted by half-sandwich iridium complexes using ammonium formate as both the nitrogen and hydride source. To optimize this method for green chemical synthesis, we tested various carbonyl substrates in common polar solvents at physiological temperature (37 °C) and ambient pressure. We found that in methanol, excellent selectivity for the amine over alcohol/amide products could be achieved for a broad assortment of carbonyl-containing compounds. In aqueous media, selective reduction of carbonyls to 1° amines was achieved in the absence of acids. Unfortunately, at Ir catalyst concentrations of 1 mM in water, reductive amination efficiency dropped significantly, which suggest that this catalytic methodology might be not suitable for aqueous applications where very low catalyst concentration is required (e.g., inside living cells).
METHOD OF CARBON MONOXIDE FIXATION AND METHOD OF AMINE FORMYLATION
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Paragraph 0078; 0081-0085, (2021/02/19)
The present invention relates to a method for fixing carbon monoxide in a metal-free condition and a method for formating amine using the same.
An efficient way for the: N -formylation of amines by inorganic-ligand supported iron catalysis
Wu, Zhikang,Zhai, Yongyan,Zhao, Wenshu,Wei, Zheyu,Yu, Han,Han, Sheng,Wei, Yongge
supporting information, p. 737 - 741 (2020/02/25)
The first example of an inorganic-ligand supported iron(iii) catalysed coupling of formic acid and amines to form formamides is reported. The pure inorganic catalyst (NH4)3[FeMo6O18(OH)6] (1), which consists of a central FeIII single-atomic core supported within a cycle-shaped inorganic ligand consisting of six MoVIO6 octahedra, shows excellent activity and selectivity, and avoids the use of complicated/commercially unavailable organic ligands. Various primary amines and secondary amines have been successfully transformed into the corresponding formamides under mild conditions, and the formylation of primary diamines has also been achieved for the first time. The Fe catalyst 1 can be reused several times without appreciable loss of activity.
Metal-free Carbon Monoxide (CO) Capture and Utilization: Formylation of Amines
Noh, Hyeong-Wan,An, Youngjoon,Lee, Seulchan,Jung, Jaehoon,Son, Seung Uk,Jang, Hye-Young
supporting information, (2019/04/26)
The capture and utilization of CO by 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) were performed in the absence of transition-metal complexes. The reaction of TBD with CO afforded TBD-CO adducts, which were converted to formylated TBD (TBD-CHO). TBD-CO adducts may include an interaction of CO with positively charged species based on NMR and IR analysis. In the presence of amines, CO was transferred from TBD-CO to amines, producing formylated amines with good yields. The reaction mechanism involving TBD-CO adducts is presented based on theoretical calculations. (Figure presented.).
