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Development of new estradiol-cationic lipid hybrids: Ten-carbon twin chain cationic lipid is a more suitable partner for estradiol to elicit better anticancer activity
The present study illustrates the synthesis and anticancer evaluation of six, ten, twelve and fourteen carbon chain containing cationic lipidated-estradiol hybrids. Previously, we have established the lipidation strategy to introduce anticancer activities in various pharmacophores including estradiol (ES). In this structure activity study the length of the carbon chain is narrowed down between C6-C14 to screen out the most potent anticancer molecule among the class. Among the newly developed ES-cationic lipid conjugates, ten-carbon chain containing derivative, ES-C10 (5c) exhibited 4-12 folds better anticancer activity than the previously established derivative, ES-C8 (5b) in various cancer cells of different origin. Moreover cytotoxicity of this molecule was not observed in non-cancer cells. Notably, in spite of bearing estrogenic moiety, ES-C10 exhibited anticancer activity irrespective of estrogen receptor (ER) expression status. ES-C10 exhibited prominent sub-G0 arrest of cancer cells with concomitant induction of apoptosis and demonstrated significant inhibition of tumor growth in mouse melanoma model. Collectively, ES-C10 exemplifies the development of an anticancer agent with broader activity against cancer cells of different origins.
Sudhakar, Godeshala,Bathula, Surendar Reddy,Banerjee, Rajkumar
p. 653 - 663
(2014)
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Hoerr,Harwood,Ralston
(1946)
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Chemoselective transfer hydrogenation of nitriles to secondary amines with nickel(II) catalysts
Herein we report the selective transfer hydrogenation (TH) of nitriles to secondary (2°) amines with simple Ni(II)-catalysts using ammonia borane (AB) as a source of hydrogen (H2). A bis(pyrazolylmethyl)pyridine (L1) or ethylenediamine (L4) ligated Ni(II) pre-catalyst, created in situ, could hydrogenate several aromatic- and aliphatic nitriles in full conversions and isolated yields of up to 88% under ambient temperature and in very short reaction times. Deuterium labelling experiments illustrated the incorporation of a proton on the nitrogen and hydride on the α-carbon of dibenzylamine. Using α-picoline borane, containing no dissociable protons, assisted with the postulation of a two-step TH mechanism of benzonitrile. AB was subjected to dehydrogenation and it was observed that a maximum of 2.96 equivalents of H2 gas could be generated from NiCl2?6H2O/L1.
Vermaak, Vincent,Vosloo, Hermanus C.M.,Swarts, Andrew J.
(2021/07/25)

Highly Selective Hydrogenative Conversion of Nitriles into Tertiary, Secondary, and Primary Amines under Flow Reaction Conditions
Flow reaction methods have been developed to selectively synthesize tertiary, secondary, and primary amines depending on heterogeneous platinum-group metal species under catalytic hydrogenation conditions using nitriles as starting materials. A 10 % Pd/C-packed catalyst cartridge affords symmetrically substituted tertiary amines in good to excellent yields. A 10 % Rh/C-packed catalyst cartridge enables the divergent synthesis of secondary and primary amines, with either cyclohexane or acetic acid as a solvent, respectively. Reaction parameters, such as the metal catalyst, solvent, and reaction temperature, and continuous-flow conditions, such as flow direction and second support of the catalyst in a catalyst cartridge, are quite important for controlling the reaction between the hydrogenation of nitriles and nucleophilic attack of in situ-generated amines to imine intermediates. A wide variety of aliphatic and aromatic nitriles could be highly selectively transformed into the corresponding tertiary, secondary, and primary amines by simply changing the metal species of the catalyst or flow parameters. Furthermore, the selective continuous-flow methodologies are applied over at least 72 h to afford three different types of amines in 80–99 % yield without decrease in catalytic activities.
Furugen, Chikara,Ito, Naoya,Jiang, Jing,Park, Kwihwan,Sajiki, Hironao,Shimizu, Eisho,Yamada, Tsuyoshi
(2021/12/13)

One-pot reductive amination of carboxylic acids: a sustainable method for primary amine synthesis
The reductive amination of carboxylic acids is a very green, efficient and sustainable method for the production of (bio-based) amines. However, with current technology, this reaction requires two to three reaction steps. Here, we report the first (heterogeneous) catalytic system for the one-pot reductive amination of carboxylic acids to amines, with solely H2 and NH3 as the reactants. This reaction can be performed with relatively cheap ruthenium-tungsten bimetallic catalysts in the green and benign solvent cyclopentyl methyl ether (CPME). Selectivities of up to 99% for the primary amine could be achieved at high conversions. Additionally, the catalyst is recyclable and tolerant for common impurities such as water and cations (e.g. sodium carboxylate).
Coeck, Robin,De Vos, Dirk E.
supporting information
p. 5105 - 5114
(2020/08/25)

A multifaceted role of a mobile bismuth promoter in alcohol amination over cobalt catalysts
Promotion with small amounts of different elements is an efficient strategy for the enhancement of the performance of many heterogeneous catalysts. Supported cobalt catalysts exhibit significant activity in the synthesis of primary amines via alcohol amination with ammonia, which is an economically efficient and environmentally friendly process. Insufficient selectivity to primary amines, low activity and fast cobalt catalyst deactivation remain serious issues restricting the application of alcohol amination in the industry. In this work, we have discovered the multifaceted role of the bismuth promoter, which is highly mobile under reaction conditions, in 1-octanol amination over supported cobalt catalysts. First, the overall reaction rate was enhanced more than twice on promotion with bismuth. Second, the selectivity to primary amines increased 6 times in the presence of Bi at high alcohol conversion. Finally, the bismuth promotion resulted in extremely high stability of the cobalt catalyst. Characterization by XRD, temperature programmed reduction, STEM, CO chemisorption, BET, TGA and FTIR has showed that the enhancement of the catalytic performance on promotion with bismuth is due to better cobalt reducibility, easy removal of strongly adsorbed intermediates and products by the mobile promoter and suppression of amine coupling reactions resulting in secondary and tertiary amines.
Bahri, Mounib,Ersen, Ovidiu,Khodakov, Andrei Y.,Kusema, Bright T.,Niu, Feng,Ordomsky, Vitaly V.,Yan, Zhen
p. 4270 - 4278
(2020/07/14)

Amination of aliphatic alcohols with urea catalyzed by ruthenium complexes: effect of supporting ligands
In the present study, ruthenium-catalyzed amination of alcohols by urea as a convenient ammonia carrier in the presence of free diphosphine ligands has been described. A number of ruthenium-phosphine complexes have been studied among which, [(Cp)RuCl(dppe)] was found as an efficient catalyst for alcohol amination reaction. The crystal structures of two new half-sandwich ruthenium complexes, [(Cp)RuCl(dppe)] and [(C6H6)RuCl2(PHEt2)], were determined by X-ray crystallographic analysis. Also the effect of using different supporting phosphines, ratio of raw materials and reaction temperature on conversion and selectivity was investigated. Under optimum reaction conditions high conversion (98percent) and chemo-selectivity toward secondary amines were obtained.
Dindar, Sara,Nemati Kharat, Ali
(2020/09/02)

Nanoceria-promoted low Pd-Ni catalyst for the synthesis of secondary amines from aliphatic alcohols and ammonia
This paper describes the preparation of a series of bimetallic Pd-Ni catalysts supported over nanoceria with very low Ni and Pd loading (2-TPR, H2-TPD, STEM-EDS-SDD and XPS. The sequence of impregnation of both metals and the Pd loading affected to an important extent the catalytic activity by conditioning the crystallite size and the Pd and Ni speciation, as well as the reducibility and reversible H2 storage properties. By optimizing the preparation protocols, a 0.5wt% Pd-0.5wt% Ni-Pd/CeO2 formulation prepared by sequential impregnation of the nickel and palladium precursors afforded 80% yield of dioctylamine at almost full conversion [TON = 1160 mmol per mmol (Ni + Pd)surface] in the direct amination reaction of 1-octanol with ammonia at 180 °C for 2 h. Metal leaching during the reaction could be completely avoided. The high catalytic performance of Pd-Ni induced by nanoceria places this catalyst among the best ever reported catalysts for the synthesis of secondary amines.
Fang,Yan,Vits,Southward,Pera-Titus
p. 1215 - 1230
(2019/03/12)

Sustainable hydrogenation of aliphatic acyclic primary amides to primary amines with recyclable heterogeneous ruthenium-tungsten catalysts
The hydrogenation of amides is a straightforward method to produce (possibly bio-based) amines. However current amide hydrogenation catalysts have only been validated in a rather limited range of toxic solvents and the hydrogenation of aliphatic (acyclic) primary amides has rarely been investigated. Here, we report the use of a new and relatively cheap ruthenium-tungsten bimetallic catalyst in the green and benign solvent cyclopentyl methyl ether (CPME). Besides the effect of the Lewis acid promotor, NH3 partial pressure is identified as the key parameter leading to high primary amine yields. In our model reaction with hexanamide, yields of up to 83% hexylamine could be achieved. Beside the NH3 partial pressure, we investigated the effect of the catalyst support, PGM-Lewis acid ratio, H2 pressure, temperature, solvent tolerance and product stability. Finally, the catalyst was characterized and proven to be very stable and highly suitable for the hydrogenation of a broad range of amides.
Coeck, Robin,Berden, Sarah,De Vos, Dirk E.
supporting information
p. 5326 - 5335
(2019/10/11)

Selective Transformations of Triglycerides into Fatty Amines, Amides, and Nitriles by using Heterogeneous Catalysis
The use of triglycerides as an important class of biomass is an effective strategy to realize a more sustainable society. Herein, three heterogeneous catalytic methods are reported for the selective one-pot transformation of triglycerides into value-added chemicals: i) the reductive amination of triglycerides into fatty amines with aqueous NH3 under H2 promoted by ZrO2-supported Pt clusters; ii) the amidation of triglycerides under gaseous NH3 catalyzed by high-silica H-beta (Hβ) zeolite at 180 °C; iii) the Hβ-promoted synthesis of nitriles from triglycerides and gaseous NH3 at 220 °C. These methods are widely applicable to the transformation of various triglycerides (C4–C18 skeletons) into the corresponding amines, amides, and nitriles.
Jamil, Md. A. R.,Siddiki, S. M. A. Hakim,Touchy, Abeda Sultana,Rashed, Md. Nurnobi,Poly, Sharmin Sultana,Jing, Yuan,Ting, Kah Wei,Toyao, Takashi,Maeno, Zen,Shimizu, Ken-ichi
p. 3115 - 3125
(2019/04/26)

N-Methylation of amines and nitroarenes with methanol using heterogeneous platinum catalysts
We report herein the selective N-methylation of amines and nitroarenes with methanol under basic conditions using carbon-supported Pt nanoparticles (Pt/C) as a heterogeneous catalyst. This method is widely applicable to four types of N-methylation reactions: (1) N,N-dimethylation of aliphatic amines under N2, (2) N-monomethylation of aliphatic amines under 40 bar H2, (3) N-monomethylation of aromatic amines under N2, and (4) tandem synthesis of N-methyl anilines from nitroarenes and methanol under 2 bar H2. All these reactions under the same catalytic system showed high yields of the corresponding methylamines for a wide range of substrates, high turnover number (TON), and good catalyst reusability. Mechanistic studies suggested that the reaction proceeded via a borrowing hydrogen methodology. Kinetic results combined with density functional theory (DFT) calculations revealed that the high performance of Pt/C was ascribed to the moderate metal–hydrogen bond strength of Pt.
Jamil, Md.A.R.,Touchy, Abeda S.,Rashed, Md. Nurnobi,Ting, Kah Wei,Siddiki, S.M.A. Hakim,Toyao, Takashi,Maeno, Zen,Shimizu, Ken-ichi
p. 47 - 56
(2019/02/07)

PROCESS FOR PREPARING AN AMINE VIA A DIRECT AMINATION REACTION
This invention provides a process for preparing an amine by direct amination of alcohols in the presence of CD assisted catalyst, notably permitting then to produce aliphatic amines by aliphatic alcohols.
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(2018/09/21)

PROCESS FOR PREPARING AMINE VIA DIRECT AMINATION REACTION
Disclosed is an effective process for converting alcohols to an amine, notably primary, with desired characteristics such as inexpensiveness, high selectivity and conversion. Specifically, the reaction is performed in the presence of a low loading transition metal catalyst, notably noble metal-free metal.
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(2018/08/26)

Direct Synthesis of Lactams from Keto Acids, Nitriles, and H2 by Heterogeneous Pt Catalysts
We report herein the first general catalytic system for the direct synthesis of N-substituted γ- and δ-lactams by reductive amination/cyclization of keto acids (including levulinic acid) with nitriles and H2 under mild conditions (7 bar H2, 110 °C, solvent free). The most effective catalyst, Pt and MoOx co-loaded TiO2 (Pt-MoOx/TiO2), shows a wide substrate scope, high turnover number (TON), and good reusability.
Siddiki,Touchy, Abeda S.,Bhosale, Ashvini,Toyao, Takashi,Mahara, Yuji,Ohyama, Junya,Satsuma, Atsushi,Shimizu, Ken-Ichi
p. 789 - 795
(2018/02/27)

Conversion of Primary Amines to Symmetrical Secondary and Tertiary Amines using a Co-Rh Heterobimetallic Nanocatalyst
Symmetrical tertiary amines have been efficiently realized from amine and secondary amines via deaminated homocoupling with heterogeneous bimetallic Co2Rh2/C as catalyst (molar ratio Co:Rh=2:2). Unsymmetric secondary anilines were produced from the reaction of anilines with symmetric tertiary amines. The Co2Rh2/C catalyst exhibited very high catalytic activity towards a wide range of amines and could be conveniently recycled ten times without considerable leaching. (Figure presented.).
Chung, Hyunho,Han, Seulgi,Chung, Young Keun,Park, Ji Hoon
supporting information
p. 1267 - 1272
(2018/02/12)

Colloid and Nanosized Catalysts in Organic Synthesis: XVIII.1 Disproportionation and Cross-Coupling of Amines During Catalysis with Immobilized Nickel Nanoparticles
It has been stated that immobilized nickel nanoparticles catalyze disproportionation and cross-coupling of amines. The influence of the support on the catalysis of these properties in the in plug-flow reactor has been studied. The use of active carbon as the support has been found advantageous for the cross-coupling of amines, whereas alumina was a better support for the disproportionation reaction.
Popov, Yu. V.,Mokhov,Latyshova,Nebykov,Panov,Davydova
p. 2757 - 2761
(2018/02/21)

PRODUCTION OF AMINES UTILIZING ZEOLITE CATALYSTS
The present invention concerns a process for forming a primary or a secondary amine via amination reaction comprising: reacting an alcohol with an amine in the presence of a zeolite comprising a transition metal chosen in the group consisting of Group 8 to 12 elements of the Periodic Table and any combination thereof.
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(2017/09/27)

Mixed oxides supported low-nickel formulations for the direct amination of aliphatic alcohols with ammonia
The present study focuses on the selective synthesis of primary amines from aliphatic alcohols and ammonia using alumina-ceria supported nickel formulations based on very low nickel loading (≤2 wt%) and without any additive or external H2 supply. The effect of the catalyst preparation methods and modes of nickel impregnation were studied in detail and comprehensively characterized. The best formulation afforded 80% n-octanol conversion with 78% selectivity to n-octylamine at optimized reaction conditions, which were far better than control catalysts and benchmark Ni-alumina formulations relying on high Ni loadings. The enhanced activities of the alumina-ceria supported nickel catalysts was attributed to three combined effects: (1) a higher reducibility of surface nickel oxide species, (2) the genesis of very small and homogeneously distributed nickel nanoparticles (2–3 nm), and (3) a strong decline in the formation of nickel aluminates. Furthermore, unlike benchmark Ni catalysts, these formulations afforded a higher resistance to leaching.
Tomer,Yan,Ponchel,Pera-Titus
p. 133 - 146
(2017/11/03)

Nitrile hydrogenation using nickel nanocatalysts in ionic liquids
Ni nanoparticles (NPs) embedded in imidazolium based ionic liquids (ILs) have been proven to be versatile catalysts for the selective hydrogenation of benzonitrile to benzylamine with good recyclability in a biphasic system. Influence of the used ILs and reaction conditions has been examined in detail and a wider substrate scope has been studied using benzonitrile derivatives and aliphatic nitriles.
Konnerth, Hannelore,Prechtl, Martin H. G.
supporting information
p. 9594 - 9597
(2017/09/18)

Ruthenium-Catalyzed Deaminative Hydrogenation of Aliphatic and Aromatic Nitriles to Primary Alcohols
The deaminative hydrogenation of nitriles towards alcohols is a useful reaction to transform nitriles into alcohols with NH3 as the sole byproduct. Using the simple and robust RuHCl(CO)(PPh3)3 complex as a catalyst, at low H2 pressures a series of aliphatic and aromatic nitriles could be transformed into the corresponding alcohols. Suitable solvent systems for these reactions were 1,4-dioxane/water and EtOH/water mixtures. In most cases, the selectivity for the alcohols was excellent, and the corresponding amines were formed only in trace amounts.
Molnár, István Gábor,Calleja, Pilar,Ernst, Martin,Hashmi, A. Stephen K.,Schaub, Thomas
p. 4175 - 4178
(2017/10/09)

Facile preparation of Ni/Al2O3 catalytic formulations with the aid of cyclodextrin complexes: Towards highly active and robust catalysts for the direct amination of alcohols
A series of Ni/Al2O3 catalysts with variable Ni loading (2–20 wt%) were prepared by aqueous wet impregnation of a nitrate precursor using native cyclodextrins as metal complex hosts. The impact of β-CD was carefully characterized at different stages of the preparation by a set of complementary techniques including TG-MS analysis, mass spectrometry, X-ray diffraction, temperature-programmed reduction, CO pulse chemisorption, X-ray photoelectron spectroscopy and electron microscopy. It was found that the use of cyclodextrins afforded a much higher Ni dispersion and narrower distribution of Ni particle sizes, as well as a much higher availability of reduced surface Ni species. As a result, the cyclodextrin-assisted catalysts exhibited enhanced catalytic properties in the direct amination of benzyl alcohol with aniline and 1-octanol with ammonia, both operated via the hydrogen borrowing mechanism. Furthermore, the use of cyclodextrins allowed a significant improvement of the robustness of the catalysts by mitigating the nickel leaching during reaction.
Tomer, Ajay,Wyrwalski, Frédéric,Przybylski, Cédric,Paul, Jean-Fran?ois,Monflier, Eric,Pera-Titus, Marc,Ponchel, Anne
p. 111 - 124
(2017/11/03)

An improved and one-pot procedure to the synthesis of symmetric amines by domino reactions of 5-methyl-1,3,4-thiadiazole-2-amine, a new nitrogen atom donor, and alkyl halides
Abstract: A new one-pot method has been introduced in this work for the synthesis of symmetrical primary, secondary, and tertiary alkyl amines from alkyl halides and 5-methyl-1,3,4-thiadiazole-2-amine as a nitrogen-transfer reagent. In this method, all three types of amines have been successfully prepared after changing the ratio of substrates and base control. In addition to the introduction of a new nitrogen-transfer reagent, other important features of this work include normal atmospheric conditions and excellent yields under mild reaction conditions.
Soleiman-Beigi, Mohammad,Mohammadi, Fariba
p. 2123 - 2128
(2017/10/26)

Pushing the Limits of Neutral Organic Electron Donors: A Tetra(iminophosphorano)-Substituted Bispyridinylidene
A new ground-state organic electron donor has been prepared that features four strongly π-donating iminophosphorano substituents on a bispyridinylidene skeleton. Cyclic voltammetry reveals a record redox potential of ?1.70 V vs. saturated calomel electrode (SCE) for the couple involving the neutral organic donor and its dication. This highly reducing organic compound can be isolated (44 %) or more conveniently generated in situ by a deprotonation reaction involving its readily prepared pyridinium ion precursor. This donor is able to reduce a variety of aryl halides, and, owing to its redox potential, was found to be the first organic donor to be effective in the thermally induced reductive S N bond cleavage of N,N-dialkylsulfonamides, and reductive hydrodecyanation of malonitriles.
Hanson, Samuel S.,Doni, Eswararao,Traboulsee, Kyle T.,Coulthard, Graeme,Murphy, John A.,Dyker, C. Adam
supporting information
p. 11236 - 11239
(2016/07/06)

Cobalt-Catalyzed Synthesis of Aromatic, Aliphatic, and Cyclic Secondary Amines via a "hydrogen-Borrowing" Strategy
The replacement of precious metals with inexpensive, less toxic, and earth-abundant elements in typical noble-metal-mediated organic transformations is a major goal in current synthetic chemistry and industries. The metal-catalyzed N-alkylation of amines with other amines through a "hydrogen-borrowing" principle represents a green and atom-economical reaction for the synthesis of secondary amines. However, catalysts developed thus far that are effective for this process remain quite scarce and are only limited to a few ruthenium and iridium complexes. In this work, we present a cobalt-catalyzed selective alkylation of amines with amines to synthesize a large variety of secondary amines. A range of amine substrates have been converted to the corresponding products through hetero- or homocoupling between amines. Cyclic sec-amines are also achieved from diamine precursors as rare examples.
Yin, Zhiwei,Zeng, Haisu,Wu, Jing,Zheng, Shengping,Zhang, Guoqi
p. 6546 - 6550
(2016/10/14)

Esters, Including Triglycerides, and Hydrogen as Feedstocks for the Ruthenium-Catalyzed Direct N-Alkylation of Amines
Triglycerides are used for the direct N-alkylation of amines with molecular hydrogen for the first time. A broad range of interesting and industrially relevant secondary and tertiary amines are obtained in the presence of an in situ formed Ru/Triphos complex. Notably, plant oil can be efficiently applied in this single-step process. Moreover, a variety of other methyl esters can be used as N-alkylation agents in the presence of hydrogen for the synthesis of more advanced building blocks.
Adam, Rosa,Cabrero-Antonino, Jose R.,Junge, Kathrin,Jackstell, Ralf,Beller, Matthias
supporting information
p. 11049 - 11053
(2016/10/13)

Photochemical Cleavage of Benzylic C-N Bond to Release Amines
The 3-(diethylamino)benzyl (DEABn) group has been studied for releasing primary, secondary, and tertiary amines by direct photochemical breaking of the benzylic C-N bond. While photochemical release of primary and secondary amines provides high yields in
Wang, Pengfei,Devalankar, Dattatray A.,Lu, Wenya
p. 6195 - 6200
(2016/08/16)

Colloid and nanosized catalysts in organic synthesis: XIV. Reductive amination and amidation of carbonitriles catalyzed by nickel nanoparticles
Hydrogenation of carbonitriles catalyzed by nickel nanoparticles in the presence of primary amines led to the predominant formation of unsymmetrical secondary amines. In the presence of secondary amines hydrogenation of nitrites provided enamines as main products. Hydrogenation of nitriles in the presence of formamide or acetamide afforded formyl or acetyl derivatives of primary amines.
Popov, Yu. V.,Mokhov,Shcherbakova
p. 798 - 805
(2016/06/13)

Triphos derivatives and diphosphines as ligands in the ruthenium-catalysed alcohol amination with NH3
The ruthenium-triphos and diphosphine-catalysed amination of alcohols with ammonia is reported. Various types of triphos derivatives with electron-donating functional group were synthesized and used as ligands in the Ru-catalysed alcohol amination with NH3. The triphos derivatives are effective for the formation of primary amines. On the other hand, if hemilabile diphosphines as tridentate ligands are used, mixtures of secondary-along with primary amines are obtained. It was found that even simple diphosphines can be used as ligands for the selective formation of the secondary amines. The diphosphine system allows a new entry to the Ru-catalysed formation of secondary amines.
Nakagawa,Derrah,Schelwies,Rominger,Trapp,Schaub
p. 6856 - 6865
(2016/05/19)

Selective Activation of Alcohols in the Presence of Reactive Amines over Intermetallic PdZn: Efficient Catalysis for Alcohol-Based N-Alkylation of Various Amines
Pd-based intermetallic compounds supported on Al2O3 (PdxMy/Al2O3, where M = Bi, Cu, Fe, Ga, In, Pb, Sn, or Zn) were prepared and tested as catalysts for the selective activation of alcohols in the presence of reactive amines, which is highly challenging and is the key strategy for alcohol-based N-alkylation of amines. Although the Pd/Al2O3 catalyst exhibited a high catalytic activity, undesired side reactions such as amine dimerization (via amine activation) and C-O bond scission occurred, resulting in a poor yield of the N-alkylation product. In contrast, the PdZn/Al2O3 catalyst acted as an efficient catalyst for this reaction, displaying high catalytic activities, selectivities, and atom efficiencies and a wide substrate scope. Detailed kinetic and computational studies revealed that the relative affinity of Pd for alcohol and amine drastically changes by the formation of a PdZn intermetallic phase. On monometallic Pd, the adsorption and activation of amines are preferred over those of alcohols in terms of thermodynamic and kinetic aspects, respectively. However, this trend is inverted on PdZn, allowing preferential adsorption and activation of alcohols and, hence, selective N-alkylation.
Furukawa, Shinya,Suzuki, Ryohei,Komatsu, Takayuki
p. 5946 - 5953
(2016/09/09)

A ruthenium racemisation catalyst for the synthesis of primary amines from secondary amines
A Ru-based half sandwich complex used in amine and alcohol racemization reactions was found to be active in the splitting of secondary amines to primary amines using NH3. Conversions up to 80% along with very high selectivities were achieved. However, after about 80% conversion the catalyst lost activity. Similar to Shvo's catalyst, the complex might deactivate under the influence of ammonia. It was revealed that not NH3 but mainly the primary amine is responsible for the deactivation.
Pingen, Dennis,Altinta?, ?i?dem,Rudolf Schaller, Max,Vogt, Dieter
p. 11765 - 11771
(2016/07/28)

Method of producing higher amine (by machine translation)
PROBLEM TO BE SOLVED: To provide a method of producing a secondary or tertiary higher amine. SOLUTION: The method of producing a higher amine comprises allowing a primary or secondary amine to react with an alcohol in the presence of at least one species of hydrogen halide selected from hydrogen chloride, hydrogen bromide and hydrogen iodide, or in the presence of a compound capable of producing a hydrogen halide (such as 1,3,5-triazo-2,4,6-triphosphorine-2,2,4,4,6,6-chloride). If the raw material amine is a primary amine, a secondary higher amine and a tertiary higher amine can be produced. If the raw material amine is a secondary amine, a tertiary higher amine can be produced. COPYRIGHT: (C)2012,JPO&INPIT
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Paragraph 0048; 0073; 0079

(2016/10/08)

Gamma-radiolytic stability of new methylated TODGA derivatives for minor actinide recycling
The stability against gamma radiation of MeTODGA (methyl tetraoctyldiglycolamide) and Me2TODGA (dimethyl tetraoctyldiglycolamide), derivatives from the well-known extractant TODGA (N,N,N′,N′-tetraoctyldiglycolamide), were studied and compared. Solutions of MeTODGA and Me2TODGA in alkane diluents were subjected to 60Co γ-irradiation in the presence and absence of nitric acid and analyzed using LC-MS to determine their rates of radiolytic concentration decrease, as well as to identify radiolysis products. The results of product identification from three different laboratories are compared and found to be in good agreement. The diglycolamide (DGA) concentrations decreased exponentially with increasing absorbed dose. The MeTODGA degradation rate constants (dose constants) were uninfluenced by the presence of nitric acid, but the acid increased the rate of degradation for Me2TODGA. The degradation products formed by irradiation are also initially produced in greater amounts in acid-contacted solution, but products may also be degraded by continued radiolysis. The identified radiolysis products suggest that the weakest bonds are those in the diglycolamide center of these molecules.
Galn, Hitos,Zarzana, Christopher A.,Wilden, Andreas,Nez, Ana,Schmidt, Holger,Egberink, Richard J. M.,Leoncini, Andrea,Cobos, Joaqun,Verboom, Willem,Modolo, Giuseppe,Groenewold, Gary S.,Mincher, Bruce J.
p. 18049 - 18056
(2015/10/28)

Ru(II)-triphos catalyzed amination of alcohols with ammonia via ionic species
An active and selective system for the amination of primary alcohols to primary amines with ammonia based on ruthenium and triphos as the tridentate phosphine ligand was developed. On the basis of detailed mechanistic studies, we propose that the active catalyst is, unlike the previously reported systems on this reaction, a cationic ruthenium complex. The experimental findings are supported by detailed density functional theory (DFT) calculations on the catalytic cycle. Because of the cationic nature of the active catalyst, strong anion and solvent effects were observed in the catalytic amination reaction when using the ruthenium triphos complexes. Therefore, a higher activity could be achieved when the nonpolar solvent toluene is used in this amination instead of tetrahydrofuran. Our findings can help to develop and optimize the system systematically for an application to relevant target molecules.
Derrah, Eric J.,Hanauer, Matthias,Plessow, Philipp N.,Schelwies, Mathias,Da Silva, Marion K.,Schaub, Thomas
p. 1872 - 1881
(2015/06/08)

Metal-free aerobic oxidative C-N bond cleavage of tertiary amines for the synthesis of N-heterocycles with high atom efficiency
An efficient metal-free aerobic oxidative C-N bond cleavage of tertiary amines has been developed to construct N-heterocycles using molecular oxygen as the sole oxidant with high atom efficiency, in which all of the three alkyl groups in tertiary amines can be utilized and transformed into N-heterocycles. This journal is the Partner Organisations 2014.
Chen, Xiuling,Chen, Tieqiao,Zhou, Yongbo,Han, Daoqing,Han, Li-Biao,Yin, Shuang-Feng
supporting information
p. 3802 - 3807
(2014/06/09)

Metal-free reductive cleavage of C-N and S-N bonds by photoactivated electron transfer from a neutral organic donor
A photoactivated neutral organic super electron donor cleaves challenging arenesulfonamides derived from dialkylamines at room temperature. It also cleaves a)ArC-NR and b)ArN-C bonds. This study also highlights the assistance given to these cleavage reactions by the groups attached to N in (a) and to C in (b), by lowering LUMO energies and by stabilizing the products of fragmentation. Radical fragmentations: Electron transfer from the photoactivated neutral electron donor 1 delivers high yields of S-N and C-N cleavage products for a range of nitrogen-containing species. These reactions proceed at room temperature and under mild reaction conditions in the absence of any metal reagents. DMF=N,N-dimethylformamide, Ts=4-toluenesulfonyl.
O'Sullivan, Steven,Doni, Eswararao,Tuttle, Tell,Murphy, John A.
supporting information
p. 474 - 478
(2014/01/23)

Alcohol amination with ammonia catalyzed by an acridine-based ruthenium pincer complex: A mechanistic study
The mechanistic course of the amination of alcohols with ammonia catalyzed by a structurally modified congener of Milstein's well-defined acridine-based PNP-pincer Ru complex has been investigated both experimentally and by DFT calculations. Several key Ru intermediates have been isolated and characterized. The detailed analysis of a series of possible catalytic pathways (e.g., with and without metal-ligand cooperation, inner- and outer-sphere mechanisms) leads us to conclude that the most favorable pathway for this catalyst does not require metal-ligand cooperation.
Ye, Xuan,Plessow, Philipp N.,Brinks, Marion K.,Schelwies, Mathias,Schaub, Thomas,Rominger, Frank,Paciello, Rocco,Limbach, Michael,Hofmann, Peter
p. 5923 - 5929
(2014/05/20)

PROCESS FOR PREPARING AMINES BY HOMOGENEOUSLY CATALYZED ALCOHOL AMINATION IN THE PRESENCE OF A COMPLEX CATALYST COMPRISING IRIDIUM AND AN AMINO ACID
The invention relates to a process for preparing amines (A) by alcohol amination of alcohols (Al) by means of an aminating agent (Am) with elimination of water, wherein the alcohol amination is carried out in the presence of a complex catalyst comprising iridium and an amino acid.
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Paragraph 0140-0142

(2014/03/21)

Alcohol amination with heterogeneous ruthenium hydroxyapatite catalysts
The intermolecular amination of alcohols was performed with ruthenium (Ru3+) immobilized on a calcium hydroxyapatite support. No additional base additives were necessary, nor did the catalyst require base treatment prior to reaction. High conversions were obtained with different amine and alcohol reactants.
Peeters, Annelies,Claes, Laurens,Geukens, Inge,Stassen, Ivo,De Vos, Dirk
p. 191 - 197
(2013/11/19)

Heterogeneously catalyzed self-condensation of primary amines to secondary amines by supported copper catalysts
Self-condensation of primary amines to symmetrically substituted secondary amines could efficiently be promoted by an inexpensive supported copper catalyst, Cu/Al2O3, easily prepared by the reduction of the hydroxide precursor, Cu(OH)x/Al2O3. Various kinds of structurally diverse primary amines including benzylamine, picolylamine, and aliphatic amine derivatives could selectively be converted into the corresponding secondary amines in moderate to excellent yields without any cocatalysts such as bases and stabilizing ligands in 1 atm of Ar or H 2. The reactions in H2 showed higher selectivities to desired secondary amines than those in Ar. The roles of H2 are the promotion of hydrogenation of N-alkylimines and the stabilization of active Cu(0) species. In addition, in the presence of Cu/Al2O3, unsymmetrically substituted secondary amines could efficiently be synthesized by N-alkylation of primary amines with alcohols and reductive amination of aldehydes. The observed catalysis was truly heterogeneous, and the retrieved Cu/Al2O3 catalyst could be reused for self-condensation without a significant loss of its catalytic performance. The reaction mechanism involving dehydrogenation of primary amines and condensation to N-alkylimines followed by hydrogenation, the so-called "borrowing hydrogen pathway", has been proposed. The Royal Society of Chemistry 2013.
Kim, Insu,Itagaki, Shintaro,Jin, Xiongjie,Yamaguchi, Kazuya,Mizuno, Noritaka
p. 2397 - 2403
(2013/09/02)

Oxidant-free conversion of primary amines to nitriles
An amide-derived NNN-Ru(II) hydride complex catalyzes oxidant-free, acceptorless, and chemoselective dehydrogenation of primary and secondary amines to the corresponding nitriles and imines with liberation of dihydrogen. The catalyst system tolerates oxidizable functionality and is selective for the dehydrogenation of primary amines (-CH2NH2) in the presence of amines without α-CH hydrogens.
Tseng, Kuei-Nin T.,Rizzi, Andrew M.,Szymczak, Nathaniel K.
supporting information
p. 16352 - 16355
(2013/12/04)

Development of a general non-noble metal catalyst for the benign amination of alcohols with amines and ammonia
The N-alkylation of amines or ammonia with alcohols is a valuable route for the synthesis of N-alkyl amines. However, as a potentially clean and economic choice for N-alkyl amine synthesis, non-noble metal catalysts with high activity and good selectivity are rarely reported. Normally, they are severely limited due to low activity and poor generality. Herein, a simple NiCuFeOx catalyst was designed and prepared for the N-alkylation of ammonia or amines with alcohol or primary amines. N-alkyl amines with various structures were successfully synthesized in moderate to excellent yields in the absence of organic ligands and bases. Typically, primary amines could be efficiently transformed into secondary amines and N-heterocyclic compounds, and secondary amines could be N-alkylated to synthesize tertiary amines. Note that primary and secondary amines could be produced through a one-pot reaction of ammonia and alcohols. In addition to excellent catalytic performance, the catalyst itself possesses outstanding superiority, that is, it is air and moisture stable. Moreover, the magnetic property of this catalyst makes it easily separable from the reaction mixture and it could be recovered and reused for several runs without obvious deactivation. Copyright
Cui, Xinjiang,Dai, Xingchao,Deng, Youquan,Shi, Feng
supporting information
p. 3665 - 3675
(2013/03/29)

Heterogeneous Ni catalyst for direct synthesis of primary amines from alcohols and ammonia
This paper reports the synthesis of primary amines from alcohols and NH3 by an Al2O3-supported Ni nanoparticle catalyst as the first example of heterogeneous and noble-metal-free catalytic system for this reaction without additional hydrogen sources under relatively mild conditions. Various aliphatic alcohols are tolerated, and turnover numbers were higher than those of Ru-based homogeneous catalysts. The catalyst was recoverable and was reused. The effects of the Ni oxidation states and the acid-base nature of support oxides on the catalytic activity are studied. It is clarified that the surface metallic Ni sites are the catalytically active species, and the copresence of acidic and basic sites on the support surface is also indispensable for this catalytic system.
Shimizu, Ken-Ichi,Kon, Kenichi,Onodera, Wataru,Yamazaki, Hiroshi,Kondo, Junko N.
p. 112 - 117
(2013/03/29)

Selective alkylation of amines with alcohols by Cp*- iridium(III) half-sandwich complexes
[Cp*Ir(Pro)Cl] (Pro = prolinato) was identified among a series of Cp*-iridium half-sandwich complexes as a highly reactive and selective catalyst for the alkylation of amines with alcohols. It is active under mild conditions in either toluene or water without the need for base or other additives, tolerates a wide range of alcohols and amines, and gives secondary amines in good to excellent isolated yields.
Wetzel, Alexander,Woeckel, Simone,Schelwies, Mathias,Brinks, Marion K.,Rominger, Frank,Hofmann, Peter,Limbach, Michael
p. 266 - 269
(2013/03/14)

Metal-free reductive cleavage of benzylic esters and ethers: Fragmentations result from single and double electron transfers
The mechanisms for the reductive cleavage of benzylic esters and ethers by neutral organic electron donor 1 are different (see scheme). Products isolated from the cleavage of benzylic ethers result from the transfer of two electrons, without the intermediacy of benzyl radicals, which are believed to be intermediates in the reductive cleavage of benzylic esters. Copyright
Doni, Eswararao,O'Sullivan, Steven,Murphy, John A.
supporting information
p. 2239 - 2242
(2013/03/28)

A general approach to substituted benzimidazoles and benzoxazoles via heterogeneous palladium-catalyzed hydrogen-transfer with primary amines
The synthesis of benzimidazoles starting from o-phenylenediamines and amines in the presence of palladium on charcoal as catalyst is reported. Under microwave dielectric heating it is possible to use a tertiary, a secondary, and even a primary amine as the substrate for a palladium-mediated process to get 2-substituted or 1,2-disubstituted benzimidazoles, depending on the nature of the o-phenylenediamine employed. Primary amines are the most suitable reagents for the atom economy of the overall process that resulted to be general as several different substituted benzimidazoles were obtained in good yield. Benzoxazoles can be also prepared starting from primary amines and o-aminophenol. The reaction is also highly selective as no (poly)-alkylated phenylenediamines or cross-contaminated benzimidazoles are obtained starting from N-monoalkylphenylenediamines. This behavior was interpreted as a scarce aptitude to dehydrogenation of the methylene bonded to the aromatic NH of N-alkylarylamines. The experiments carried out consent to draw an almost complete picture of the reaction pathways occurring during the process. The catalyst can be recycled several times and, although far from optimal performances, catalyst TON=90 is encouraging for further large-scale optimization protocols. In addition, the palladium on charcoal-catalyzed microwave-assisted reaction of o-phenylenediamine gives de-alkylation of tertiary amines and transformation into the secondary ones. Copyright
Pizzetti, Marianna,De Luca, Elisa,Petricci, Elena,Taddei, Maurizio,Porcheddu, Andrea
p. 2453 - 2464,12
(2012/12/12)

A general approach to substituted benzimidazoles and benzoxazoles via heterogeneous palladium-catalyzed hydrogen-transfer with primary amines
The synthesis of benzimidazoles starting from o-phenylenediamines and amines in the presence of palladium on charcoal as catalyst is reported. Under microwave dielectric heating it is possible to use a tertiary, a secondary, and even a primary amine as the substrate for a palladium-mediated process to get 2-substituted or 1,2-disubstituted benzimidazoles, depending on the nature of the o-phenylenediamine employed. Primary amines are the most suitable reagents for the atom economy of the overall process that resulted to be general as several different substituted benzimidazoles were obtained in good yield. Benzoxazoles can be also prepared starting from primary amines and o-aminophenol. The reaction is also highly selective as no (poly)-alkylated phenylenediamines or cross-contaminated benzimidazoles are obtained starting from N-monoalkylphenylenediamines. This behavior was interpreted as a scarce aptitude to dehydrogenation of the methylene bonded to the aromatic NH of N-alkylarylamines. The experiments carried out consent to draw an almost complete picture of the reaction pathways occurring during the process. The catalyst can be recycled several times and, although far from optimal performances, catalyst TON=90 is encouraging for further large-scale optimization protocols. In addition, the palladium on charcoal-catalyzed microwave-assisted reaction of o-phenylenediamine gives de-alkylation of tertiary amines and transformation into the secondary ones. Copyright
Pizzetti, Marianna,De Luca, Elisa,Petricci, Elena,Porcheddu, Andrea,Taddei, Maurizio
p. 2453 - 2464
(2013/01/14)

Hydrolysis and radiation stability of m-xylylene bis-diglycolamide: Synthesis and quantitative study of degradation products by HPLC-APCI +
For nuclear hydrometallurgical separation process development, it is necessary to demonstrate the stability of the extracting systems, since it is well known that radio- and hydrolytic degradation leads to undesirable effects, such as a decrease in selectivity, poorer phase separation and third-phase formation. Recently, we have developed a new family of bis-diglycolamide (bis-DGA) molecules with high distribution coefficients (D) for EuIII over AmIII. One of these bis-DGA extractants, namely, compound 1, showed high distribution coefficients even under gamma irradiation at 1000 kGy with external 60Co sources. We report herein a detailed account on the stability of 1 against radio- and hydrolysis. We have also identified and quantified the sub-products formed during the irradiation process. Qualitative and quantitative analyses of irradiated 1 were performed by HPLC-MS, indicating the presence of seventeen degradation compounds. All fragments (2-18) were identified and synthesized independently. To complete this study, the An III and LnIII extraction properties of these fragments were assessed under the same experimental conditions as those used to evaluate the AnIII and LnIII extraction by irradiated 1. Despite the significance of a decrease in the concentration of 1, Am/Eu D values are still quite high. This means that at least some degradation products also act as efficient extractants. It is relevant to remark that two of the major degradation products (compounds 3 and 11) are stable to radiation and showed high D values for AmIII and EuIII extraction. Compound 1, an extractant of AmIII and EuIII from nuclear waste, was irradiated with γ irradiation at 1000 kGy with external 60Co sources, resulting in 17 subproducts. These compounds were synthesized and qualitative and quantitative analyses of irradiated 1 were performed. Two of the major degradation products were stable to radiation and showed high D values for AmIII and EuIII extraction. Copyright
Galan, Hitos,Murillo, Maria Teresa,Sedano, Rosa,Nunez, Ana,De Mendoza, Javier,Gonzalez-Espartero, Amparo,Prados, Pilar
experimental part
p. 3959 - 3969
(2011/09/15)

Structure-activity study to develop cationic lipid-conjugated haloperidol derivatives as a new class of anticancer therapeutics
Haloperidol (HP), a neuroleptic drug, shows high affinity toward-receptors (SR). HP and reduced-HP at higher concentration were known to induce apoptosis in SR-overexpressing carcinomas and melanomas. Herein, we report the development of cationic lipid-conjugated haloperidol as a new class of anticancer therapeutics. In comparison to HP, the C-8 carbon chain analogue (HP-C8) showed significantly high, SR-assisted antiproliferative activity against cancer cells via caspase-3-mediated apoptosis and down-regulation of pAkt. Moreover, melanoma tumor aggressiveness in HP-C8-treated mice was significantly lower than that in HP-treated mice. HP-C8 simultaneously reduced Akt-protein level and increased Bax/Bcl-2 ratio in vascular endothelial cells, thereby indicating a possible protein kinase down-regulatory and apoptosis inducing role in tumor-associated vascular cells. In conclusion, we developed-receptor-targeting cationic lipid-modified HP derivatives as a promising class of anticancer therapeutic that concurrently affects cancer and tumor environment associated angiogenic vascular cells through induction of apoptosis and Akt protein down-regulation.
Pal, Krishnendu,Pore, Subratakumar,Sinha, Sutapa,Janardhanan, Rajiv,Mukhopadhyay, Debabrata,Banerjee, Rajkumar
experimental part
p. 2378 - 2390
(2011/06/11)

Synthesis of primary amines from secondary and tertiary amines: Ruthenium-catalyzed amination using ammonia
Splitting of secondary and tertiary amines! The first selective catalytic synthesis of primary amines from secondary and tertiary amines with ammonia is reported. The products are obtained in yields up to 84 %. Copyright
Baehn, Sebastian,Imm, Sebastian,Neubert, Lorenz,Zhang, Min,Neumann, Helfried,Beller, Matthias
experimental part
p. 4705 - 4708
(2011/05/12)

Reductions of challenging organic substrates by a nickel complex of a noninnocent crown carbene ligand
The first crown-tetracarbene complex of Ni(II) has been prepared, and its crystal structure determined. The complex can be reduced by Na/Hg, with an uptake of two electrons. The reduced complex reductively cleaves arenesulfonamides, including those derived from secondary aliphatic amines, and effects Birch reduction of anthracenes as well as reductive cleavage of stilbene oxides. Computational studies show that the orbital that receives electrons upon reduction of the complex 2 is predominantly based on the crown carbene ligand and also that the HOMO of the parent complex 2 is based on the ligand.
Findlay, Neil J.,Park, Stuart R.,Schoenebeck, Franziska,Cahard, Elise,Zhou, Sheng-Ze,Berlouis, Leonard E. A.,Spicer, Mark D.,Tuttle, Tell,Murphy, John A.
supporting information; experimental part
p. 15462 - 15464
(2011/02/22)

Selective deprotection of methanesulfonamides to amines
"Chemical Equation Presented" Methanesulfonamldes were deprotected to their parent amines via deprotonation and oxygenation with O 2 (g), even in the presence of other traditional sulfonamides.
Naito, Hiroyuki,Hata, Takeshi,Urabe, Hirokazu
experimental part
p. 1228 - 1230
(2010/06/13)