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Surface properties of Ni/MgO catalysts for the hydrogenation of lauronitrile
60%Ni/MgO (wt%) catalysts were prepared by the co-precipitation method and the influence of n-butanol treatment was investigated. The results showed that the treatment with n-butanol improved the dispersion and reducibility of supported nickel, resulted in an increase of H2 uptake from 410 to 582 μmol/g, corresponding to an increase of active Ni surface area from 32 to 46 m2/g (increased by 42%). Accordingly, the catalytic activity for the hydrogenation of toluene to methyl cyclohexane was significantly increased. Microcalorimetric adsorption of H2 and CO indicated that the treatment with n-butanol increased the amount of active metal sites on the surface, without the change of electron densities of supported nickel surface. Microcalorimetric adsorption of CO2 and NH3 revealed the strong surface basicity and weak surface acidity for the Ni/MgO catalysts, especially for the reduced ones. The initial heat for the adsorption of acetonitrile was measured to be about 130 kJ/mol on the Ni/MgO catalysts, indicating the strong interaction between acetonitrile and the supported nickel, which might be an important factor determining the activity of nickel for the hydrogenation of aliphatic nitriles. The surface basicity of the Ni/MgO catalysts might play a role in inhibiting the formation of secondary and tertiary amines and therefore improved the selectivity to primary amine during the hydrogenation of lauronitrile to laurylamine. In addition, the Ni/MgO-B catalyst prepared with n-butanol treatment seemed more active for the hydrogenation of lauronitrile.
Chen, Hui,Xue, Mingwei,Shen, Jianyi
p. 246 - 255
(2010)
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Physical and chemical properties of N-(2-hydroxyethyl)alkylamines
Physical and chemical properties of N-(2-hydroxyethyl)alkylamines were studied, isotherms of a surface tension of homologous series of these compounds on a liquid-gas interface in water and hydrochloric acid were obtained. Pleiades Publishing, Ltd., 2010.
Radushev,Koltashev,Nasrtdinova,Shcherban,Chekanova,Plotnikova
p. 1475 - 1479
(2010)
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Efficient hydrogenation of aliphatic amides to amines over vanadium-modified rhodium supported catalyst
This work presents a highly efficient catalytic hydrogenation system developed for the selective transformation of tertiary N,N-dimethyldodecanamide and secondary azepan-2-one amides to the corresponding amines. Industrial hydrogenation catalysts Pd/Al2O3, Pt/Al2O3 and Rh/Al2O3 were modified with vanadium (V) or molybdenum (Mo) species as oxophilic centres. The modified catalysts were prepared by deposition of V or Mo precursor on supported catalysts via impregnation method. The catalysts were characterized by ICP-OES, XRD, XPS, H2-TPR, FTIR, CO-chemisorption, TEM, SEM-EDX and TGA. Modified Rh-V/Al2O3 catalyst displayed the best performance affording high yield and selectivity >95 % to the desired tertiary and secondary amines at moderate reaction conditions of T H2 0 sites and oxophilic Vδ+ sites in the bimetallic Rh-V/Al2O3 catalyst were determined to be beneficial for the selective dissociation of C[dbnd]O bond of the carboxamides into the desired amines.
Hernandez, Willinton Y.,Kusema, Bright T.,Pennetier, Alex,Streiff, Stéphane
(2021/08/19)

Direct Enzymatic Synthesis of Fatty Amines from Renewable Triglycerides and Oils
Fatty amines represent an important class of commodity chemicals which have broad applicability in different industries. The synthesis of fatty amines starts from renewable sources such as vegetable oils or animal fats, but the process has multiple drawbacks that compromise the overall effectiveness and efficiency of the synthesis. Herein, we report a proof-of-concept biocatalytic alternative towards the synthesis of primary fatty amines from renewable triglycerides and oils. By coupling a lipase with a carboxylic acid reductase (CAR) and a transaminase (TA), we have accomplished the direct synthesis of multiple medium and long chain primary fatty amines in one pot with analytical yields as high as 97 %. We have also performed a 75 mL preparative scale reaction for the synthesis of laurylamine from trilaurin, obtaining 73 % isolated yield.
Bevinakatti, Han,Citoler, Joan,Finnigan, William,Turner, Nicholas J.
(2021/11/30)

SUPPORTED HETEROGENEOUS CATALYST, PREPARATION AND USE THEREOF
A supported heterogeneous catalyst comprises rhodium and vanadium on a support, wherein the supported heterogeneous catalyst is preparable by depositing vanadium on a supported rhodium catalyst by impregnation. A process for preparing the aforementioned catalyst and a process for converting an amide into an amine in the presence of the aforementioned catalyst are provided.
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(2021/06/11)

PROCESS FOR CONVERTING AMIDE TO AMINE
Provided is a process for converting an amide into an amine comprising hydrogenation of the amide at a temperature not higher than 130°C and a hydrogen pressure not higher than 50 bar in the presence of a supported heterogeneous catalyst preparable by a method comprising depositing vanadium on a supported noble metal catalyst by impregnation.
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(2021/06/11)

MATERIALS COMPRISING CARBON-EMBEDDED COBALT NANOPARTICLES, PROCESSES FOR THEIR MANUFACTURE, AND USE AS HETEROGENEOUS CATALYSTS
The present invention relates to catalytically active material, comprising grains of non-graphitizing carbon with cobalt nanoparticles dispersed therein, wherein dP, the average diameter of cobalt nanoparticles in the non-graphitizing carbon grains, is in the range of 1 nm to 20 nm, D, the average distance between cobalt nanoparticles in the non-graphitizing carbon grains, is in the range of 2 nm to 150 nm, and ω, the combined total mass fraction of metal in the non-graphitizing carbon grains, is in the range of 30 wt% to 70 wt% of the total mass of the non-graphitizing carbon grains, and wherein dP, D and ω conform to the following relation: 4.5 dP / ω > D ≥ 0.25 dP / ω. The present invention, further, relates to a process for the manufacture of material according to the invention, as well as its use as a catalyst.
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(2021/03/13)

MATERIALS COMPRISING CARBON-EMBEDDED IRON NANOPARTICLES, PROCESSES FOR THEIR MANUFACTURE, AND USE AS HETEROGENEOUS CATALYSTS
201900257 Ausland 18 Abstract The present invention relates to catalytically active material, comprising grains of non-graphitizing carbon with iron nanoparticles dispersed therein, wherein dp, the average diameter of iron nanoparticles in the non-graphitizing carbon grains, is in the range of 1 nm to 20 nm, D, the average distance between iron nanoparticles in the non-graphitizing carbon grains, is in the range 5 of 2 nm to 150 nm, and ω, the combined total mass fraction of metal in the non-graphitizing carbon grains, is in the range of 30 wt% to 70 wt% of the total mass of the non-graphitizing carbon grains, and wherein dp, D and ω conform to the following relation: 4.5 dp / ω > D ≥ 0.25 dp / ω. The present invention, further, relates to a process for the manufacture of material according to the invention, as well as its use as a catalyst. 10
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(2021/03/13)

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)

ENVIRONMENTALLY-FRIENDLY HYDROAZIDATION OF OLEFINS
The present invention provides processes for the synthesis of organic azides, intermediates for the production thereof, and compositions related thereto.
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(2020/01/24)

A biocatalytic cascade for the conversion of fatty acids to fatty amines
Fatty amine synthesis from renewable sources is an energetically-demanding process involving toxic metal catalysts and harsh reaction conditions as well as selectivity problems. Herein we present a mild, biocatalytic alternative to the conventional amination of fatty acids through a one-pot tandem cascade performed by a carboxylic acid reductase (CAR) and a transaminase (ω-TA). Saturated and unsaturated fatty acids, with carbon chain lengths ranging from C6 to C18, were successfully aminated obtaining conversions of up to 96%.
Citoler, Joan,Derrington, Sasha R.,Galman, James L.,Bevinakatti, Han,Turner, Nicholas J.
supporting information
p. 4932 - 4935
(2019/09/30)

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)

Corresponding amine nitrile and method of manufacturing thereof
The invention relates to a manufacturing method of nitrile. Compared with the prior art, the manufacturing method has the characteristics of significantly reduced using amount of an ammonia source, low environmental pressure, low energy consumption, low production cost, high purity and yield of a nitrile product and the like, and nitrile with a more complex structure can be obtained. The invention also relates to a method for manufacturing corresponding amine from nitrile.
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(2018/05/07)

Efficient access to unprotected primary amines by iron-catalyzed aminochlorination of alkenes
Primary amines are essential constituents of biologically active molecules and versatile intermediates in the synthesis of drugs and agrochemicals. However, their preparation from easily accessible alkenes remains challenging. Here, we report a general strategy to access primary amines from alkenes through an operationally simple iron-catalyzed aminochlorination reaction. A stable hydroxylamine derivative and benign sodium chloride act as the respective nitrogen and chlorine sources. The reaction proceeds at room temperature under air; tolerates a large scope of aliphatic and conjugated alkenes, including densely functionalized substrates; and provides excellent anti-Markovnikov regioselectivity with respect to the amino group. The reactivity of the 2-chloroalkylamine products, an understudied class of amphoteric molecules, enables facile access to linear or branched aliphatic amines, aziridines, aminonitriles, azido amines, and homoallylic amines.
Legnani, Luca,Prina-Cerai, Gabriele,Delcaillau, Tristan,Willems, Suzanne,Morandi, Bill
p. 434 - 439
(2018/11/21)

Cobalt-based nanoparticles prepared from MOF-carbon templates as efficient hydrogenation catalysts
The development of efficient and selective nanostructured catalysts for industrially relevant hydrogenation reactions continues to be an actual goal of chemical research. In particular, the hydrogenation of nitriles and nitroarenes is of importance for the production of primary amines, which constitute essential feedstocks and key intermediates for advanced chemicals, life science molecules and materials. Herein, we report the preparation of graphene shell encapsulated Co3O4- and Co-nanoparticles supported on carbon by the template synthesis of cobalt-terephthalic acid MOF on carbon and subsequent pyrolysis. The resulting nanoparticles create stable and reusable catalysts for selective hydrogenation of functionalized and structurally diverse aromatic, heterocyclic and aliphatic nitriles, and as well as nitro compounds to primary amines (>65 examples). The synthetic and practical utility of this novel non-noble metal-based hydrogenation protocol is demonstrated by upscaling several reactions to multigram-scale and recycling of the catalyst.
Murugesan, Kathiravan,Senthamarai, Thirusangumurugan,Sohail, Manzar,Alshammari, Ahmad S.,Pohl, Marga-Martina,Beller, Matthias,Jagadeesh, Rajenahally V.
p. 8553 - 8560
(2018/11/30)

Structure-Function Relationship in Ester Hydrogenation Catalyzed by Ruthenium CNN-Pincer Complexes
A series of six pincer-ruthenium complexes has been synthesized and applied in the catalytic hydrogenation of esters. The ruthenium complexes have the formula Ru(pincer)HCl(CO), where the CNN-pincer ligands feature N-heterocyclic carbene (NHC), pyridine, and dialkylamino donor groups. Through systematic variation of the steric bulk of the NHC substituent and the amine substituents, a clear structure-function relationship emerges. The most active catalysts in this series feature the bulkiest NHC substituent employed, 2,6-diisopropylphenyl. For the dialkylamino group, catalysts substituted with isopropyl or ethyl groups were the most active, while catalysts substituted with methyl groups were significantly less active. The most active catalyst discovered catalyzes the complete hydrogenation of a range of esters at loadings of 0.05-0.2 mol %.
Le, Linh,Liu, Jiachen,He, Tianyi,Kim, Daniel,Lindley, Eric J.,Cervarich, Tia N.,Malek, Jack C.,Pham, John,Buck, Matthew R.,Chianese, Anthony R.
p. 3286 - 3297
(2018/09/27)

Selective Hydrogenation of Nitriles to Primary Amines by using a Cobalt Phosphine Catalyst
A general procedure for the catalytic hydrogenation of nitriles to primary amines by using a non-noble metal-based system is presented. Co(acac)3 in combination with tris[2-(dicyclohexylphosphino)ethyl]phosphine efficiently catalyzes the selective hydrogenation of a wide range of (hetero)aromatic and aliphatic nitriles to give the corresponding amines.
Adam, Rosa,Bheeter, Charles Beromeo,Cabrero-Antonino, Jose R.,Junge, Kathrin,Jackstell, Ralf,Beller, Matthias
p. 842 - 846
(2017/03/17)

Selective Catalytic Hydrogenations of Nitriles, Ketones, and Aldehydes by Well-Defined Manganese Pincer Complexes
Hydrogenations constitute fundamental processes in organic chemistry and allow for atom-efficient and clean functional group transformations. In fact, the selective reduction of nitriles, ketones, and aldehydes with molecular hydrogen permits access to a green synthesis of valuable amines and alcohols. Despite more than a century of developments in homogeneous and heterogeneous catalysis, efforts toward the creation of new useful and broadly applicable catalyst systems are ongoing. Recently, Earth-abundant metals have attracted significant interest in this area. In the present study, we describe for the first time specific molecular-defined manganese complexes that allow for the hydrogenation of various polar functional groups. Under optimal conditions, we achieve good functional group tolerance, and industrially important substrates, e.g., for the flavor and fragrance industry, are selectively reduced.
Elangovan, Saravanakumar,Topf, Christoph,Fischer, Steffen,Jiao, Haijun,Spannenberg, Anke,Baumann, Wolfgang,Ludwig, Ralf,Junge, Kathrin,Beller, Matthias
supporting information
p. 8809 - 8814
(2016/07/29)

NOVEL LIPIDS AND LIPID NANOPARTICLE FORMULATIONS FOR DELIVERY OF NUCLEIC ACIDS
Compounds are provided having the following structure: (I) or a pharmaceutically acceptable salt, tautomer or stereoisomer thereof, wherein R1a, R1b, R2a, R2b, R3a, R3b, R4a, R4b, R5, R6, R7, R8, R9, L1, L2, a, b, c, d and e are as defined herein. Use of the compounds as a component of lipid nanoparticle formulations for delivery of a therapeutic agent, compositions comprising the compounds and methods for their use and preparation are also provided.
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(2016/05/02)

Hydrogenation of Aliphatic and Aromatic Nitriles Using a Defined Ruthenium PNP Pincer Catalyst
Selective catalytic reductions of nitriles are presented using the commercially available Ru-Macho-BH complex. A variety of aliphatic, aromatic and (hetero)cyclic nitriles including industrially important adipodinitrile are hydrogenated to the corresponding primary amines. Modelling suggests the reaction follows an outer sphere hydrogenation mechanism. An efficient and selective catalytic reduction of nitriles is presented using the commercially available Ru-Macho-BH complex. A variety of aliphatic, aromatic and (hetero)cyclic nitriles including the industrially important adipodinitrile are hydrogenated to the corresponding primary amines. The reaction follows an outer-sphere mechanism.
Neumann, Jacob,Bornschein, Christoph,Jiao, Haijun,Junge, Kathrin,Beller, Matthias
supporting information
p. 5944 - 5948
(2015/09/22)

Highly chemoselective reduction of amides (primary, secondary, tertiary) to alcohols using SmI2/amine/H2O under mild conditions
Highly chemoselective direct reduction of primary, secondary, and tertiary amides to alcohols using SmI2/amine/H2O is reported. The reaction proceeds with C-N bond cleavage in the carbinolamine intermediate, shows excellent functional group tolerance, and delivers the alcohol products in very high yields. The expected C-O cleavage products are not formed under the reaction conditions. The observed reactivity is opposite to the electrophilicity of polar carbonyl groups resulting from the nX → πC=O (X = O, N) conjugation. Mechanistic studies suggest that coordination of Sm to the carbonyl and then to Lewis basic nitrogen in the tetrahedral intermediate facilitate electron transfer and control the selectivity of the C-N/C-O cleavage. Notably, the method provides direct access to acyl-type radicals from unactivated amides under mild electron transfer conditions.
Szostak, Michal,Spain, Malcolm,Eberhart, Andrew J.,Procter, David J.
supporting information
p. 2268 - 2271
(2014/03/21)

METHOD FOR PRODUCING N-SUBSTITUTED AMINE COMPOUNDS THROUGH CATALYZED ALKYLATION
The invention relates to a method for producing a N-substituted amine compound by catalyzed alkylation. The method uses amine and alcohol or two kinds of amines as the reaction materials, employs composite metal oxides catalyst at a reaction temperature of 80-180° C. to catalyze the reaction for 6-36 hours, so as to produce the N-substituted amine compound. The reaction condition of the method of the invention is relatively moderate, using a catalyst made of cheap non-noble metals, which is non-caustic and easy to be separated and reused. The reaction does not need any medium and has relatively high conversion rate and selectivity.
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(2014/02/16)

Electron transfer reduction of nitriles using SmI2-Et 3N-H2O: Synthetic utility and mechanism
The first general reduction of nitriles to primary amines under single electron transfer conditions is demonstrated using SmI2 (Kagan's reagent) activated with Lewis bases. The reaction features excellent functional group tolerance and represents an attractive alternative to the use of pyrophoric alkali metal hydrides. Notably, the electron transfer from Sm(II) to CN functional groups generates imidoyl-type radicals from bench stable nitrile precursors.
Szostak, Michal,Sautier, Brice,Spain, Malcolm,Procter, David J.
supporting information
p. 1092 - 1095
(2014/03/21)

Ruthenium/imidazolylphosphine catalysis: Hydrogenation of aliphatic and aromatic nitriles to form amines
A convenient and efficient catalyst system for the hydrogenation of aliphatic nitriles towards the corresponding primary amines in high to excellent yields is presented. In addition, aromatic nitriles are reduced smoothly, too. The use of low catalyst loadings and molecular hydrogen make this protocol an attractive methodology. It's not complicated: A general and easy homogeneous catalyst system based on [Ru(cod)(methylallyl)2] and a cyclohexyl-substituted imidazolylphosphine ligand for selective hydrogenation of aliphatic nitriles is presented. In addition, by using an isopropyl-substituted imidazolylphosphine ligand, selected aromatic nitriles were reduced with excellent yields towards the primary amine. Furthermore, two new crystal structures give an insight of possible pre-catalysts.
Werkmeister, Svenja,Junge, Kathrin,Wendt, Bianca,Spannenberg, Anke,Jiao, Haijun,Bornschein, Christoph,Beller, Matthias
supporting information
p. 4227 - 4231
(2014/05/06)

Rational design of a transition state analogue with picomolar affinity for pseudomonas aeruginosa PvdQ, a siderophore biosynthetic enzyme
The Pseudomonas aeruginosa enzyme PvdQ can process different substrates involved in quorum-sensing or in siderophore biosynthesis. Substrate selectivity was evaluated using steady-state kinetic constants for hydrolysis of N-acyl-homoserine lactones (HSLs) and p-nitrophenyl fatty acid esters. PvdQ prefers substrates with alkyl chains between 12 and 14 carbons long that do not bear a 3-oxo substitution and is revealed here to have a relatively high specificity constant for selected N-acyl-HSLs (kcat/KM = 105 to 106 M-1 s-1). However, endogenous P. aeruginosa N-acyl-HSLs are ≥100-fold disfavored, supporting the conclusion that PvdQ was not primarily evolved to regulate endogenous quorum-sensing. PvdQ plays an essential biosynthetic role for the siderophore pyoverdine, on which P. aeruginosa depends for growth in iron-limited environments. A series of alkylboronate inhibitors was found to be reversible, competitive, and extremely potent (Ki ≥ 190 pM). A 1.8 A X-ray structure shows that 1-tridecylboronic acid forms a monocovalent bond with the N-terminal β-chain Ser residue in the PvdQ heterodimer, mimicking a reaction transition state. This boronic acid inhibits growth of P. aeruginosa in iron-limited media, reproducing the phenotype of a genetic pvdQ disruption, although co-administration of an efflux pump inhibitor is required to maintain growth inhibition. These findings support the strategy of designing boron-based inhibitors of siderophore biosynthetic enzymes to control P. aeruginosa infections.
Clevenger, Kenneth D.,Wu, Rui,Er, Joyce A. V.,Liu, Dali,Fast, Walter
p. 2192 - 2200
(2013/11/06)

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
p. 3665 - 3675
(2013/03/29)

Redox self-sufficient biocatalyst network for the amination of primary alcohols
Driving the machinery: A biocatalytic redox-neutral cascade for the preparation of terminal primary amines from primary alcohols at the expense of ammonia has been established in a one-pot one-step method (see picture). Applying this artificial biocatalyst network, long-chain 1,ω-alkanediols were converted into diamines, which are building blocks for polymers, in up to 99 % conversion. Copyright
Sattler, Johann H.,Fuchs, Michael,Tauber, Katharina,Mutti, Francesco G.,Faber, Kurt,Pfeffer, Jan,Haas, Thomas,Kroutil, Wolfgang
supporting information
p. 9156 - 9159
(2012/10/30)

Ceric ammonium nitrate-mediated detritylation of tritylated amines
Efficient deprotection of tritylated amines to the corresponding amines mediated by 20 mol % ceric ammonium nitrate [Ce(NH4) 2(NO3)6, CAN], 10 equiv of acetic acid and 15 equiv of water in dichloromethane is presented. This method equally worked well in the case of morpholino nucleosides.
Pattanayak, Sankha,Sinha, Surajit
experimental part
p. 34 - 37
(2011/02/25)

Amide hydrolysis reaction catalyzed by KF/Al2O3 under microwave irradiation and solvent free conditions
A microwave-enhanced hydrolysis of amides utilizing KF/Al2O 3 in the absence of solvents has been developed. Amines are produced in excellent yields along with the corresponding carboxylic acids.
Zhang, Xiuli,Luo, Kai,Chen, Wei,Wang, Lei
experimental part
p. 2209 - 2212
(2012/03/11)

Chemoselective reduction of azides catalyzed by molybdenum xanthate by using phenylsilane as the hydride source
A chemoselective, neutral, and efficient strategy for the reduction of azides to corresponding amines catalyzed by dioxobis(N,N,-diethyldithiocarbamato) molybdenum complex (1, MoO2[S2CNEt2]2) in the presence of phenylsilane is discovered. This chemoselective reduction strategy tolerates a variety of reducible functional groups.
Maddani, Mahagundappa R.,Moorthy, Saravana K.,Prabhu, Kandikere R.
supporting information; experimental part
p. 329 - 333
(2010/03/01)

Reductions of aliphatic and aromatic nitriles to primary amines with diisopropylaminoborane
Diisopropylaminoborane [BH2Nf)Pr)2] in the presence of a catalytic amount of lithium borohydride (LiBH4) reduces a large variety of aliphatic and aromatic nitriles in excellent yields. BH 2NOPr)2 can be prepared by two methods: first by reacting diisopropylamineborane [(iPr)2N)BH3] with 1.1 equiv of n-butylhthium (n-BuLi) followed by methyl iodide (MeI), or reacting iPrN:BH 3 with 1 equiv of n-BuLi followed by trimethylsilyl chloride (TMSCl). BH2N(ZPr)2 prepared with MeI was found to reduce benzonitriles to the corresponding benzylamines at ambient temperatures, whereas diisopropylaminoborane prepared with TMSCl does not reduce nitriles unless a catalytic amount of a lithium ion source, such as LiBH4 or lithium tetraphenylborate (LiBPh4), is added to the reaction. The reductions of benzonitriles with one or more electron-withdrawing groups on the aromatic ring generally occur much faster with higher yields. For example, 2,4-dichlorobenzonitrile was successfully reduced to 2,4-dichlorobenzylamine in 99% yield after 5 h at 25 °C. On the other hand, benzonitriles containing electron-donating groups on the aromatic ring require refluxing in tetrahydrofuran (THF) for complete reduction. For instance, 4- methoxybenzonitrile was successfully reduced to 4-methoxybenzylamine in 80% yield. Aliphatic nitriles can also be reduced by the BH2N(iPr) 2/cat. LiBH4 reducing system. Benzyl cyanide was reduced to phenethylamine in 83% yield. BH2NOPr)2 can also reduce nitriles in the presence of unconjugated alkenes and alkynes such as the reduction of 2-hexynenitrile to hex-5-yn-l-amine in 80% yield. Unfortunately, selective reduction of a nitrile in the presence of an aldehyde is not possible as aldehydes are reduced along with the nitrile. However, selective reduction of the nitrile group at 25 °C in the presence of an ester is possible as long as the nitrile group is activated by an electron-withdrawing substituent. It should be pointed out that lithium aminoborohydrides (LABs) do not reduce nitriles under ambient conditions and behave as bases with aliphatic nitriles as well as nitriles containing acidic a-protons. Consequently, both LABs and BH2NOPr)2 are complementary to each other and offer methods for the selective reductions of multifunctional compounds.
Haddenham, Dustin,Pasumansky, Lubov,DeSoto, Jamie,Eagon, Scott,Singaram, Bakthan
supporting information; experimental part
p. 1964 - 1970
(2009/07/01)

PROCESS FOR PRODUCING NITROGEN-CONTAINING COMPOUNDS
The present invention relates to a process for producing an aliphatic amine, comprising the step of contacting a linear or branched, or cyclic aliphatic alcohol having 6 to 22 carbon atoms with ammonia and hydrogen in the presence of a catalyst formed by supporting at least (A) a ruthenium component produced by hydrolysis of a ruthenium compound on a carrier, or by further supporting, in addition to the component (A), a specific second metal component or a specific third metal component on the carrier. According to the process of the present invention, an aliphatic primary amine can be produced from an aliphatic alcohol with a high catalytic activity and a high selectivity.
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(2008/06/13)

But-2-ynylbisoxycarbonyl chloride: A novel C2-symmetric reagent for the protection of amines and amino acids
(Chemical Equation Presented) A novel C2-symmetric protecting group for amines, the but-2-ynylbisoxycarbonyl (Bbc) group, is developed, which can be deblocked with tetrathiomolybdate under neutral conditions. One equivalent of the bischloroformate, BbcCl, is used for the protection of 2 equiv of the amine. Its application in peptide synthesis is established through the synthesis of a tripeptide, and its orthogonality with Cbz, Fmoc, and Boc groups has been studied.
Ramesh,Chandrasekaran
p. 4947 - 4950
(2007/10/03)

Synthesis of 13-acylamino-huprines: Different behavior of diastereomeric 13-methanesulfonamido-huprines on PPA-mediated hydrolysis
Two diastereomeric pairs of rationally designed huprines additionally substituted at position 13 with a formamido or an acetamido group have been synthesized as potential high affinity acetylcholinesterase inhibitors. The synthetic sequence involves hydrolysis of two diastereomeric 13-methanesulfonamido-huprines, followed by acylation of the resulting diastereomeric amines. In the hydrolysis reaction, carried out with PPA under harsh conditions, significant amounts of cyclized or rearranged by-products were also formed, depending on the stereochemistry of the starting compound.
Camps, Pelayo,Gómez, Elena,Mu?oz-Torrero, Diego
p. 5423 - 5431
(2007/10/03)

A mild deprotection strategy for allyl-protecting groups and its implications in sequence specific dendrimer synthesis
A mild deprotection strategy for allyl ethers under basic conditions in the presence of a palladium catalyst is described. Under these conditions, aryl allyl ethers can be cleaved selectively in the presence of alkyl allyl ethers. These conditions are also effective in the deprotection of allyloxycarbonyl groups. The utility of the current methodology in sequence specific dendrimer synthesis is demonstrated.
Vutukuri, Dharma Rao,Bharathi, Pandi,Yu, Zhouying,Rajasekaran, Karthik,Tran, My-Huyen,Thayumanavan
p. 1146 - 1149
(2007/10/03)

A novel reduction of azides to amines with tellurium metal in near-critical water
Tellurium metal in near-critical water (275°C) provides a novel and efficient method for the reduction of azides, producing amines in good yields.
Wang, Lei,Li, Pinhua,Chen, Jianhui,Yan, Jincan
p. 1807 - 1813
(2007/10/03)

Selective reductions. Part 60: Chemoselective reduction of organyl azides with dichloroborane-dimethyl sulfide
The rate and stoichiometry of the reduction of an organyl azide with BH3·THF was examined under standardized conditions at room temperature. Borane derivatives, such as dialkyl-, alkoxy-, and haloboranes were also examined for the reduction of azides. This study revealed BHCl2·SMe2 to be the most suitable reagent for the reduction of azides. The chemoselectivity of this reagent was also studied by reducing n-hexyl azide in the presence of representative series of functional groups, including esters, halides, nitriles, and nitro groups. BHCl2·SMe2 reduces azides in the presence of all of the above functional groups as well as olefins. Taking advantage of the differences in reactivity of BHCl2·SMe2 and BH3·THF or BH3·SMe2, it is now possible to reduce selectively an azide in the presence of olefins or to hydroborate an olefin in the presence of azides by a judicious choice of the reagent.
Salunkhe, Ashok M.,Veeraraghavan Ramachandran,Brown, Herbert C.
p. 10059 - 10064
(2007/10/03)

Amino group-containing thiols and method for production thereof
These amino group-containing mono- or dithiols are represented by formula (I). In order to prepare them, ethylene sulfide is reacted with at least one compound of formula (II), the average number of moles of ethylene sulfide added corresponding to the total m+n, and possibly the compound of formula (I) as obtained is further reacted with ethylene sulfide in order to increase the value of m+n. R1 stands for a straight or branched alkyl or alkenyl group having 10 to 30 carbon atoms; R2 stands for a straight or branched alkyl or alkenyl group having 10 to 30 carbon atoms, or a —(CH2—CH2—S)n—H group; m and n, which are identical or different, each represent 0 or an integer in the range of 1 to 10 and satisfy 1.62 stands for a hydrogen atom in which case R2 in formula (I) will represent —(CH2—CH2—S)n—H, or a straight or branched alkyl or alkenyl group having 10 to 30 carbon atoms, in which case it will remain unchanged in the compound of the formula (I).
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(2008/06/13)

Cyanoguanidines as cell proliferation inhibitors
The present invention relates to hitherto unknown compounds of formula (I) or their tautomeric forms, the attachment to the pyridine being in the 3- or 4-position, in which formula R1 stands for one or more substituents which can be the same or different and are selected from the group consisting of: hydrogen, halogen, trifluoromethyl nitro, amino, cyano, carboxy, or alkyl, alkoxy, or alkoxycarbonyl, the C-content of which can be from 1 to 4; X stands for a straight or branched C9-C20 carbon chain, saturated or unsaturated or Q—Ar—R; in which formula Ar stands for phenyl, Q stands for a C5-C20 divalent hydrocarbon radical which can be straight, branched, saturated or unsaturated and R stands for hydrogen or for one or more substituents which can be the same or different and are selected from the group consisting of: hydroxy, amino, halogen, trifluoromethyl, cyano, nitro, carboxy, carbamoyl, or alkyl, alkoxy, alkylthio, alkylamino, or alkoxycarbonyl, the C-content of which can be from 1 to 4; and pharmaceutically acceptable, non-toxic salts and N-oxides thereof. The present compounds are of value in the human and veterinary practice.
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(2008/06/13)

A new novel and practical one pot methodology for conversion of alcohols to amines
A convenient and efficient one pot sequence has been developed for the transformation of alcohols to amines using sodium azide, triphenylphosphine in CCl4-DMF.
Vidya Sagar Reddy,Venkat Rao,Subramanyam,Iyengar
p. 2233 - 2237
(2007/10/03)

Wavelength-selective cleavage of photolabile protecting groups
The selective photocleavage of protecting groups using monochromatic light is described. Some groups were found to react faster than others at 254 nm, whereas this trend was reversed at 419 nm. This behavior was preserved in solution mixtures of both grou
Bochet
p. 6341 - 6346
(2007/10/03)

Convenient cleavage of water-insoluble allylic substrates in the presence of per(2,6-di-O-methyl)-β-cyclodextrin
The removal of allylic protecting groups promoted by a water soluble palladium complex of the trisulfonated triphenylphosphine is achieved in very high yields (95-100%) on a wide range of water-insoluble substrates in a genuine two-phase system by using the per(2,6-di-O-methyl)-β-cyclodextrin as inverse phase transfer catalyst. The catalytic activities were up to 1000 times higher than those observed without cyclodextrin.
Widehem, Rodrigue,Lacroix, Thibaut,Bricout, Herve,Monflier, Eric
p. 722 - 724
(2007/10/03)

Process for producing aliphatic amine derivative
The present invention provides a process for easily producing an alkylene oxide adduct to an aliphatic amine compound which has a fully excellent color, is not turbid, and does not deteriorate in color even through long-term storage. That is, the present invention provides a process for producing an alkylene oxide adduct to a primary or secondary amine compound having an aliphatic, saturated or unsaturated, hydrocarbon radical having 8 to 22 carbon atoms, having an excellent color, by reacting an alkyene oxide to the amine compound, characterized by comprising the step of adding a base or an aqueous solution thereof to the amine compound and then heating the mixture.
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(2008/06/13)

1,3,2-benzodithiazol-1-oxides as microbiocides
A description is given of novel and know 1,3,2-benzodithiazole 1-oxides of the formula (I) STR1 and of their preparation and use for protecting industrial materials against infestation by microorganisms.
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(2008/06/13)

Apparatus and method for sunless tanning
Apparatus for simulating skin tanning comprises a receptacle containing a fluid comprising dihydroxyacetone, a receptacle containing a fluid comprising a primary amine, and dispensing means for simultaneously or sequentially providing desired amount of dihydroxyacetone and amine.
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(2008/06/13)

β-carboxy sulfonamide ACAT inhibitors
β-Carboxy sulfonyl compounds of the formula STR1 wherein R1 is aryl, R3 is hydrogen or alkyl, R3 and R4 are hydrogen or alkyl, Y is --O--, --S--, or --NR2 --, and R5 is alkyl or aryl are potent inhibitors of the enzyme acyl CoA:cholesterol acyltransferase (ACAT) and are thus useful for treating hypercholesterolemia and atherosclerosis.
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(2008/06/13)

DICHLOROBORANE-DIMETHYL SULFIDE, A HIGHLY SELECTIVE REDUCING AGENT FOR REDUCTION OF ORGANYL AZIDES TO AMINES
Dichloroborane-dimethylsulfide reduces a variety of organyl azides, such as primary, secondary, tertiary, and aromatic to the corresponding amines in excellent yields.Cycloalkyl and benzylic azides are also readily reduced by this reagent.The reduction of azide with BHCl2*SMe2 is highly selective and many functional groups, such as halogen, ester, nitrile, aliphatic and armatic nitro, survice in this process.
Salunkhe, Ashok M.,Brown, Herbert C.
p. 7987 - 7990
(2007/10/02)

Selectivity control in substituted fatty amines synthesis from esters or nitriles in the presence of bifunctional catalysts
Copper chromite-type catalysts, supported by alumina or graphite and promoted with barium, were used for the one-step synthesis of tertiary fatty amines [R2NCH3 or RN(CH3)2] from ester, acid or nitrile and ammonia, methanol and hydrogen. The surface composition of the catalysts, studied by X-ray photoelectron spectroscopy and by adsorption experiments, showed that there was a correlation between selectivity and the presence of a well-dispersed CuCrO2 phase, stabilized with barium. Moreover, the elements influencing the stability of the copper catalysts were also studied, and the promoter or/and the support increased the copper surface area and the stability of the catalyst in the presence of water or ammonia.
Barrault,Brunet,Suppo-Essayem,Piccirilli,Guimon
p. 1231 - 1238
(2007/10/02)

Desulfurization with Nickel and Cobalt Boride: Scope, Selectivity, Stereochemistry, and Deuterium-Labeling Studies
A variety of organosulfur compounds containing alkylthio and arylthio groups underwent reductive desulfurization under notably mild conditions when treated with nickel boride, generated in situ from nickel chloride hexahydrate and sodium borohydride in methanol-THF (3:1).Phenyl, chloro, and ester groups are not reduced under these conditions, while iodo, bromo, nitrile, aldehyde, ketone, cyclopropane, and olefinic functions are reduced either completely or partially.Deuterium-labeling studies indicate that the hydrogen that is incorporated into the product originates from both the sodium borohydride and the protic solvent, suggesting the intermediacy of dihydrogen.The epimers 3α- and 3β-(phenylthio)cholestane afforded 3α- and 3β-deuteriocholestane, respectively, demonstrating that the reaction proceeds with retention of configuration.The method may thus be employed for the stereospecific preparation of deuterated products from organosulfur compounds.Arguments are presented in support of a tentative mechanism involving an oxidative addition-reductive elimination sequence via a nickel hydride intermediate.
Back, Thomas G.,Baron, Denise L.,Yang, Kexin
p. 2407 - 2413
(2007/10/02)