91-65-6Relevant academic research and scientific papers
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
New approach for induction of alkyl moiety to aliphatic amines by NaBH(OAc)3 with carboxylic acid
Tamura, Satoru,Sugawara, Aoi,Sato, Erika,Sato, Fuka,Sato, Keigo,Kawano, Tomikazu
supporting information, (2020/04/15)
We had found the novel N-alkylation method, which utilizes carboxylic acids as alkyl sources with sodium triacetoxyborohydride [NaBH(OAc)3]. Our methodology had been revealed to have some advantages over the reported similar procedures. Through
Photometric Characterization of the Reductive Amination Scope of the Imine Reductases from Streptomyces tsukubaensis and Streptomyces ipomoeae
Matzel, Philipp,Krautschick, Lukas,H?hne, Matthias
, p. 2022 - 2027 (2017/10/07)
Imine reductases (IREDs) have emerged as promising enzymes for the asymmetric synthesis of secondary and tertiary amines starting from carbonyl substrates. Screening the substrate specificity of the reductive amination reaction is usually performed by time-consuming GC analytics. We found two highly active IREDs in our enzyme collection, IR-20 from Streptomyces tsukubaensis and IR-Sip from Streptomyces ipomoeae, that allowed a comprehensive substrate screening with a photometric NADPH assay. We screened 39 carbonyl substrates combined with 17 amines as nucleophiles. Activity data from 663 combinations provided a clear picture about substrate specificity and capabilities in the reductive amination of these enzymes. Besides aliphatic aldehydes, the IREDs accepted various cyclic (C4–C8) and acyclic ketones, preferentially with methylamine. IR-Sip also accepted a range of primary and secondary amines as nucleophiles. In biocatalytic reactions, IR-Sip converted (R)-3-methylcyclohexanone with dimethylamine or pyrrolidine with high diastereoselectivity (>94–96 % de). The nucleophile acceptor spectrum depended on the carbonyl substrate employed. The conversion of well-accepted substrates could also be detected if crude lysates were employed as the enzyme source.
Mild N-Alkylation of Amines with Alcohols Catalyzed by the Acetate Ru(OAc)2(CO)(DiPPF) Complex
Figliolia, Rosario,Baldino, Salvatore,Nedden, Hans G.,Zanotti-Gerosa, Antonio,Baratta, Walter
supporting information, p. 14416 - 14419 (2017/10/07)
The acetate complex Ru(OAc)2(DiPPF) (2) obtained from Ru(OAc)2(PPh3)2 (1) and 1,1′-bis(diisopropylphosphino)ferrocene (DiPPF) reacts cleanly with formaldehyde affording Ru(OAc)2(CO)(DiPPF) (3) in high yield. The monocarbonyl complex 3 (0.4-2 mol %) efficiently catalyzes the N-alkylation of primary and secondary alkyl and aromatic amines using primary alcohols ROH (R=Et, nPr, nBu, PhCH2) under mild reaction conditions (30–100 °C) with an alcohol/amine molar ratio of 10-100. Formation of the monohydride RuH(OAc)(CO)(DiPPF) (4) has been observed by reaction of 3 with iPrOH in the presence of NEt3 at RT through an equilibrium reaction.
N-Alkylation of amines with phenols over highly active heterogeneous palladium hydride catalysts
Yan, Long,Liu, Xin-Xin,Fu, Yao
, p. 109702 - 109705 (2016/11/30)
Phenols are directly converted to secondary amines in considerable yield via hydrogenation and amination tandem reaction over Al2O3 supported palladium hydride (PdHx) bi-functional catalyst. Note that this system proceeds efficiently with mild conditions under H2 atmosphere, which was difficult to achieve in previous reports. The catalyst and the mechanism of reaction are both studied. Furthermore, various secondary amines can be formed in good yields under this conversion system.
Catalytic N-Alkylation of Amines Using Carboxylic Acids and Molecular Hydrogen
Sorribes, Iván,Cabrero-Antonino, Jose R.,Vicent, Cristian,Junge, Kathrin,Beller, Matthias
supporting information, p. 13580 - 13587 (2015/11/10)
A convenient, practical and green N-alkylation of amines has been accomplished by applying readily available carboxylic acids in the presence of molecular hydrogen. Applying an in situ formed ruthenium/triphos complex and an organic acid as cocatalyst, a broad range of alkylated secondary and tertiary amines are obtained in good to excellent yields. This novel method is also successfully applied for the synthesis of unsymmetrically substituted N-methyl/alkyl anilines through a direct three-component coupling reaction of the corresponding amines, carboxylic acids, and CO2 as a C1 source.
Direct catalytic N-alkylation of amines with carboxylic acids
Sorribes, Iván,Junge, Kathrin,Beller, Matthias
, p. 14314 - 14319 (2014/12/10)
A straightforward process for the N-alkylation of amines has been developed applying readily available carboxylic acids and silanes as the hydride source. Complementary to known reductive aminations, effective C-N bond construction proceeds under mild conditions and allows obtaining a broad range of alkylated secondary and tertiary amines, including fluoroalkyl-substituted anilines as well as the bioactive compound Cinacalcet HCl.
PROCESS FOR PREPARING SECONDARY AMINES IN THE LIQUID PHASE
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Paragraph 0114; 0115; 0116; 0117, (2013/07/19)
The present application relates to a process for preparing secondary amines by aminating excess primary or secondary alcohols with primary amines in the liquid phase in the presence of copper-comprising catalysts.
Selective N-alkylation of amines using nitriles under hydrogenation conditions: Facile synthesis of secondary and tertiary amines
Ikawa, Takashi,Fujita, Yuki,Mizusaki, Tomoteru,Betsuin, Sae,Takamatsu, Haruki,Maegawa, Tomohiro,Monguchi, Yasunari,Sajiki, Hironao
supporting information; experimental part, p. 293 - 304 (2012/02/01)
Nitriles were found to be highly effective alkylating reagents for the selective N-alkylation of amines under catalytic hydrogenation conditions. For the aromatic primary amines, the corresponding secondary amines were selectively obtained under Pd/C-catalyzed hydrogenation conditions. Although the use of electron poor aromatic amines or bulky nitriles showed a lower reactivity toward the reductive alkylation, the addition of NH4OAc enhanced the reactivity to give secondary aromatic amines in good to excellent yields. Under the same reaction conditions, aromatic nitro compounds instead of the aromatic primary amines could be directly transformed into secondary amines via a domino reaction involving the one-pot hydrogenation of the nitro group and the reductive alkylation of the amines. While aliphatic amines were effectively converted to the corresponding tertiary amines under Pd/C-catalyzed conditions, Rh/C was a highly effective catalyst for the N-monoalkylation of aliphatic primary amines without over-alkylation to the tertiary amines. Furthermore, the combination of the Rh/C-catalyzed N-monoalkylation of the aliphatic primary amines and additional Pd/C-catalyzed alkylation of the resulting secondary aliphatic amines could selectively prepare aliphatic tertiary amines possessing three different alkyl groups. According to the mechanistic studies, it seems reasonable to conclude that nitriles were reduced to aldimines before the nucleophilic attack of the amine during the first step of the reaction.
A novel method for N-alkylation of aliphatic amines with ethers over ?3-Al2O3
Chen, Hangeng,Zhang, Tao,Qian, Chao,Chen, Xinzhi
, p. 537 - 540 (2015/03/05)
A novel and simple method for the N-alkylation of amines with different ethers as alkylating reagents has been developed, using cheap ?3-Al2O3 as the catalyst at atmospheric pressure in the temperature range of 260-320?°C. For example, the reaction of equ
