7307-55-3Relevant academic research and scientific papers
One-pot reductive amination of carboxylic acids: a sustainable method for primary amine synthesis
Coeck, Robin,De Vos, Dirk E.
supporting information, p. 5105 - 5114 (2020/08/25)
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).
NNP-Type Pincer Imidazolylphosphine Ruthenium Complexes: Efficient Base-Free Hydrogenation of Aromatic and Aliphatic Nitriles under Mild Conditions
Adam, Rosa,Alberico, Elisabetta,Baumann, Wolfgang,Drexler, Hans-Joachim,Jackstell, Ralf,Junge, Henrik,Beller, Matthias
, p. 4991 - 5002 (2016/04/05)
A series of seven novel NImNHP-type pincer imidazolylphosphine ruthenium complexes has been synthesized and fully characterized. The use of hydrogenation of benzonitrile as a benchmark test identified [RuHCl(CO)(NImNHPtBu)] as the most active catalyst. With its stable Ru-BH4 analogue, in which chloride is replaced by BH4, a broad range of (hetero)aromatic and aliphatic nitriles, including industrially interesting adiponitrile, has been hydrogenated under mild and base-free conditions.
A Mild and Base-Free Protocol for the Ruthenium-Catalyzed Hydrogenation of Aliphatic and Aromatic Nitriles with Tridentate Phosphine Ligands
Adam, Rosa,Bheeter, Charles Beromeo,Jackstell, Ralf,Beller, Matthias
, p. 1329 - 1334 (2016/04/20)
A novel protocol for the general hydrogenation of nitriles in the absence of basic additives is described. The system is based on the combination of [Ru(cod)(methylallyl)2] (cod=cyclooctadiene) and L2. A variety of aromatic and aliphatic nitriles is hydrogenated under mild conditions (50 °C and 15 bar H2) with this system. Kinetic studies revealed higher activity in the case of aromatic nitriles compared with aliphatic ones.
Amination of ω-Functionalized Aliphatic Primary Alcohols by a Biocatalytic Oxidation-Transamination Cascade
Pickl, Mathias,Fuchs, Michael,Glueck, Silvia M.,Faber, Kurt
, p. 3121 - 3124 (2015/10/19)
Amination of non-activated aliphatic fatty alcohols to the corresponding primary amines was achieved through a five-enzyme cascade reaction by coupling a long-chain alcohol oxidase from Aspergillus fumigatus (LCAO-Af) with a ω-transaminase from Chromobacterium violaceum (ω-TA-Cv). The alcohol was oxidized at the expense of molecular oxygen to yield the corresponding aldehyde, which was subsequently aminated by the PLP-dependent ω-TA to yield the final primary amine product. The overall cascade was optimized with respect to pH, O2 pressure, substrate concentration, decomposition of H2O2 (derived from alcohol oxidation), NADH regeneration, and biocatalyst ratio. The substrate scope of this concept was investigated under optimized conditions by using terminally functionalized C4-C11 fatty primary alcohols bearing halogen, alkyne, amino, hydroxy, thiol, and nitrile groups.
Catalytic activation of hydrazine hydrate by gold nanoparticles: Chemoselective reduction of nitro compounds into amines
Gkizis, Petros L.,Stratakis, Manolis,Lykakis, Ioannis N.
, p. 48 - 51 (2013/06/27)
Supported gold nanoparticles (2NH2 as a transfer hydrogenation agent. Aryl and alkyl nitro compounds are cleanly and selectively reduced into the corresponding amines in the presence of 4 equivalents of hydrazine. The reaction tolerates other potentially reducible functionalities such as carboxylate, carbonyl, cyano or halides which remain intact.
DIVERGENT SYNTHESIS OF LOOPED POLY(ESTER)-AND POLY(ETHER)-SUBSTITUTED DENDRONS AND DENDRIMERS
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, (2010/04/30)
The present invention describes a process for preparing new looped dendrimer and dendron compounds by controlling the molar amount of branch cell reagent monomer that is combined with various cores bearing core-XR functionalities (e.g., primary, or secondary amines, thiol, or epoxy functionalities). These looped, macrocyclic structures are more robust to various conditions, with greater resistance to acid/base hydrolysis. Alternatively, the looped, macrocyclic structure may offer new orientations that would qualify it as a better chelation ligand for metals, and other similar uses.
The mechanism of dephosphorylation of bis(2,4-dinitrophenyl) phosphate in mixed micelles of cationic surfactants and lauryl hydroxamic acid
Silva, Marcelo,Mello, Renata S.,Farrukh, M. Akhyar,Venturini, Janio,Bunton, Clifford A.,Milagre, Humberto M. S.,Eberlin, Marcos N.,Fiedler, Haidi D.,Nome, Faruk
supporting information; experimental part, p. 8254 - 8260 (2010/02/28)
(Figure Presented) Mixed micelles of cetyltrimethylammonium bromide (CTABr) or dodecyltrimethylammonium bromide (DTABr) and the α-nucleophile, lauryl hydroxamic acid (LHA) accelerate dephosphorylation of bis(2,4-dinitrophenyl) phosphate (BDNPP) over the pH range 4-10. With a 0.1 mole fraction of LHA in DTABr or CTABr, dephosphorylation of BDNPP is approximately 104-fold faster than its spontaneous hydrolysis, and monoanionic LHA- is the reactive species. The results are consistent with a mechanism involving concurrent nucleophilic attack by hydroxamate ion (i) on the aromatic carbon, giving an intermediate that decomposes to undecylamine and 2,4-dinitrophenol, and (ii) at phosphorus, giving an unstable intermediate that undergoes a Lossen rearrangement yielding a series of derivatives including N,N-dialkylurea, undecylamine, undecyl isocyanate, and carbamyl hydroxamate.
Reductions of aliphatic and aromatic nitriles to primary amines with diisopropylaminoborane
Haddenham, Dustin,Pasumansky, Lubov,DeSoto, Jamie,Eagon, Scott,Singaram, Bakthan
supporting information; experimental part, p. 1964 - 1970 (2009/07/01)
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.
Radical reduction of aromatic azides to amines with triethylsilane
Benati, Luisa,Bencivenni, Giorgio,Leardini, Rino,Minozzi, Matteo,Nanni, Daniele,Scialpi, Rosanna,Spagnolo, Piero,Zanardi, Giuseppe
, p. 5822 - 5825 (2007/10/03)
Aromatic azides are inert toward triethylsilane under thermal conditions in the presence of a radical initiator, but in the presence of additional catalytic amounts of tert-dodecanethiol, they afford anilinosilanes and thence the corresponding anilines in virtually quantitative yields.
Mild and efficient reduction of azides to amines: Synthesis of fused [2,1-b]quinazolinones
Kamal, Ahmed,Ramana, K.Venkata,Ankati, Hari Babu,Ramana, A.Venkata
, p. 6861 - 6863 (2007/10/03)
FeCl3/NaI has been employed for an efficient reduction of a variety of azides. This method is selective in the presence of a nitro functionality and has been extended for the synthesis of fused [2,1-b]quinazolinone ring systems such as deoxyvasicinone.
