- Oxidation of aldehydes to acyl azides by chromic anhydride-azidotrimethylsilane
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Aldehydes are efficiently oxidized to acyl azides by azidotrimethylsilane and chromic anhydride at room temperature (aromatic), or at -10°C (aliphatic).
- Lee,Kwak
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Read Online
- Selective catalytic hydrogenation of nitriles to primary amines using iron pincer complexes
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The selective catalytic hydrogenation of nitriles to primary amines with the well-defined Fe(PNPCy) pincer complex 2 is reported. This iron pincer catalyst shows superior catalytic activity and selectivity in the reduction of various nitriles including industrially relevant adipodinitrile in high yields under relatively mild conditions.
- Lange,Elangovan,Cordes,Spannenberg,Jiao,Junge,Bachmann,Scalone,Topf,Junge,Beller
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Read Online
- Zirconium-hydride-catalyzed site-selective hydroboration of amides for the synthesis of amines: Mechanism, scope, and application
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Developing mild and efficient catalytic methods for the selective synthesis of amines is a longstanding research objective. In this respect, catalytic deoxygenative amide reduction has proven to be promising but challenging, as this approach necessitates selective C–O bond cleavage. Herein, we report the selective hydroboration of primary, secondary, and tertiary amides at room temperature catalyzed by an earth-abundant-metal catalyst, Zr-H, for accessing diverse amines. Various readily reducible functional groups, such as esters, alkynes, and alkenes, were well tolerated. Furthermore, the methodology was extended to the synthesis of bio- and drug-derived amines. Detailed mechanistic studies revealed a reaction pathway entailing aldehyde and amido complex formation via an unusual C–N bond cleavage-reformation process, followed by C–O bond cleavage.
- Han, Bo,Jiao, Haijun,Wu, Lipeng,Zhang, Jiong
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p. 2059 - 2067
(2021/09/02)
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- Selective Room-Temperature Hydrogenation of Amides to Amines and Alcohols Catalyzed by a Ruthenium Pincer Complex and Mechanistic Insight
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We report a room-temperature protocol for the hydrogenation of various amides to produce amines and alcohols. Compared with most previous reports for this transformation, which use high temperatures (typically, 100-200 °C) and H2 pressures (10-100 bar), this system proceeds under extremely mild conditions (RT, 5-10 bar of H2). The hydrogenation is catalyzed by well-defined ruthenium-PNNH pincer complexes (0.5 mol %) with potential dual modes of metal-ligand cooperation. An unusual Ru-amidate complex was formed and crystallographically characterized. Mechanistic investigations indicate that the room-temperature hydrogenation proceeds predominantly via the Ru-N amido/amine metal-ligand cooperation.
- Ben-David, Yehoshoa,Kar, Sayan,Kumar, Amit,Leitus, Gregory,Milstein, David,Rauch, Michael
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p. 5511 - 5515
(2020/07/21)
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- Synthesis of oxalamides by acceptorless dehydrogenative coupling of ethylene glycol and amines and the reverse hydrogenation catalyzed by ruthenium
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A sustainable, new synthesis of oxalamides, by acceptorless dehydrogenative coupling of ethylene glycol with amines, generating H2, homogeneously catalyzed by a ruthenium pincer complex, is presented. The reverse hydrogenation reaction is also accomplished using the same catalyst. A plausible reaction mechanism is proposed based on stoichiometric reactions, NMR studies, X-ray crystallography as well as observation of plausible intermediates.
- Ben-David, Yehoshoa,Diskin-Posner, Yael,Milstein, David,Zhou, Quan-Quan,Zou, You-Quan
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p. 7188 - 7193
(2020/07/23)
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- Facile synthesis of supported Ru-Triphos catalysts for continuous flow application in selective nitrile reduction
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The selective catalytic hydrogenation of nitriles represents an important but challenging transformation for many homogeneous and heterogeneous catalysts. Herein, we report the efficient and modular solid-phase synthesis of immobilized Triphos-type ligands in very high yields, involving only minimal work-up procedures. The corresponding supported ruthenium-Triphos catalysts are tested in the hydrogenation of various nitriles. Under mild conditions and without the requirement of additives, the tunable supported catalyst library provides selective access to both primary amines and secondary imines. Moreover, the first application of a Triphos-type catalyst in a continuous flow process is presented demonstrating high catalyst life-time over at least 195 hours without significant activity loss.
- Konrath, Robert,Heutz, Frank J.L.,Steinfeldt, Norbert,Rockstroh, Nils,Kamer, Paul C.J.
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p. 8195 - 8201
(2019/09/19)
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- Selective Hydrogenation of Nitriles to Primary Amines by using a Cobalt Phosphine Catalyst
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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
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p. 842 - 846
(2017/03/17)
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- A method of synthesizing all hair (by machine translation)
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The invention relates to a method of synthesizing all hair, which belongs to the technical field of organic synthesis. In order to market and common enanthaldehyde preparation on raw materials (enanthaldehyde preparation is castor oil cracking by-product, source sufficient), and hydroxylamine reaction generating aldoxime, aldoxime further dehydration to obtain age nitrile, the age nitrile passes through hydrogenation to obtain the hair loss. In accordance with the invention described from the enanthaldehyde preparation process to age nitrile reaction process has the advantages of simple and convenient operation, mild condition, material consumption and energy consumption and the like, and more in line with the concept of green chemical industry; the invention prepared by the hair loss not only content is high, and the quality is good, selective stability. (by machine translation)
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Paragraph 0036; 0038; 0039; 0042
(2018/03/01)
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- 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
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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
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p. 2123 - 2128
(2017/10/26)
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- Photometric Characterization of the Reductive Amination Scope of the Imine Reductases from Streptomyces tsukubaensis and Streptomyces ipomoeae
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Imine reductases (IREDs) have emerged as promising enzymes for the asymmetric synthesis of secondary and tertiary amines starting from carbonyl substrates. Screening the substrate specificity of the reductive amination reaction is usually performed by time-consuming GC analytics. We found two highly active IREDs in our enzyme collection, IR-20 from Streptomyces tsukubaensis and IR-Sip from Streptomyces ipomoeae, that allowed a comprehensive substrate screening with a photometric NADPH assay. We screened 39 carbonyl substrates combined with 17 amines as nucleophiles. Activity data from 663 combinations provided a clear picture about substrate specificity and capabilities in the reductive amination of these enzymes. Besides aliphatic aldehydes, the IREDs accepted various cyclic (C4–C8) and acyclic ketones, preferentially with methylamine. IR-Sip also accepted a range of primary and secondary amines as nucleophiles. In biocatalytic reactions, IR-Sip converted (R)-3-methylcyclohexanone with dimethylamine or pyrrolidine with high diastereoselectivity (>94–96 % de). The nucleophile acceptor spectrum depended on the carbonyl substrate employed. The conversion of well-accepted substrates could also be detected if crude lysates were employed as the enzyme source.
- Matzel, Philipp,Krautschick, Lukas,H?hne, Matthias
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p. 2022 - 2027
(2017/10/07)
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- Efficient and selective hydrogenation of amides to alcohols and amines using a well-defined manganese-PNN pincer complex
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Novel well-defined NNP and PNP manganese pincer complexes have been synthetized and fully characterized. The catalyst Mn-2 containing an imidazolyaminolphosphino ligand shows high activity and selectivity in the hydrogenation of a wide range of secondary and tertiary amides to the corresponding alcohols and amines, under relatively mild conditions. For the first time, more challenging substrates like primary aromatic amides including an actual herbicide can also be hydrogenated using this earth-abundant metal-based pincer catalyst.
- Papa, Veronica,Cabrero-Antonino, Jose R.,Alberico, Elisabetta,Spanneberg, Anke,Junge, Kathrin,Junge, Henrik,Beller, Matthias
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p. 3576 - 3585
(2017/07/11)
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- In vitro biocatalytic pathway design: Orthogonal network for the quantitative and stereospecific amination of alcohols
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The direct and efficient conversion of alcohols into amines is a pivotal transformation in chemistry. Here, we present an artificial, oxidation-reduction, biocatalytic network that employs five enzymes (alcohol dehydrogenase, NADP-oxidase, catalase, amine dehydrogenase and formate dehydrogenase) in two concurrent and orthogonal cycles. The NADP-dependent oxidative cycle converts a diverse range of aromatic and aliphatic alcohol substrates to the carbonyl compound intermediates, whereas the NAD-dependent reductive aminating cycle generates the related amine products with >99% enantiomeric excess (R) and up to >99% conversion. The elevated conversions stem from the favorable thermodynamic equilibrium (K′eq = 1.88 × 1042 and 1.48 × 1041 for the amination of primary and secondary alcohols, respectively). This biocatalytic network possesses elevated atom efficiency, since the reaction buffer (ammonium formate) is both the aminating agent and the source of reducing equivalents. Additionally, only dioxygen is needed, whereas water and carbonate are the by-products. For the oxidative step, we have employed three variants of the NADP-dependent alcohol dehydrogenase from Thermoanaerobacter ethanolicus and we have elucidated the origin of the stereoselective properties of these variants with the aid of in silico computational models.
- Knaus, Tanja,Cariati, Luca,Masman, Marcelo F,Mutti, Francesco G.
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p. 8313 - 8325
(2017/10/19)
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- NNP-Type Pincer Imidazolylphosphine Ruthenium Complexes: Efficient Base-Free Hydrogenation of Aromatic and Aliphatic Nitriles under Mild Conditions
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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.
- Adam, Rosa,Alberico, Elisabetta,Baumann, Wolfgang,Drexler, Hans-Joachim,Jackstell, Ralf,Junge, Henrik,Beller, Matthias
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supporting information
p. 4991 - 5002
(2016/04/05)
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- Stable and Inert Cobalt Catalysts for Highly Selective and Practical Hydrogenation of C≡N and C=O Bonds
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Novel heterogeneous cobalt-based catalysts have been prepared by pyrolysis of cobalt complexes with nitrogen ligands on different inorganic supports. The activity and selectivity of the resulting materials in the hydrogenation of nitriles and carbonyl compounds is strongly influenced by the modification of the support and the nitrogen-containing ligand. The optimal catalyst system ([Co(OAc)2/Phenα-Al2O3]-800 = Cat. E) allows for efficient reduction of both aromatic and aliphatic nitriles including industrially relevant dinitriles to primary amines under mild conditions. The generality and practicability of this system is further demonstrated in the hydrogenation of diverse aliphatic, aromatic, and heterocyclic ketones as well as aldehydes, which are readily reduced to the corresponding alcohols.
- Chen, Feng,Topf, Christoph,Radnik, J?rg,Kreyenschulte, Carsten,Lund, Henrik,Schneider, Matthias,Surkus, Annette-Enrica,He, Lin,Junge, Kathrin,Beller, Matthias
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supporting information
p. 8781 - 8788
(2016/08/02)
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- Selective Catalytic Hydrogenations of Nitriles, Ketones, and Aldehydes by Well-Defined Manganese Pincer Complexes
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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
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supporting information
p. 8809 - 8814
(2016/07/29)
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- A Mild and Base-Free Protocol for the Ruthenium-Catalyzed Hydrogenation of Aliphatic and Aromatic Nitriles with Tridentate Phosphine Ligands
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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.
- Adam, Rosa,Bheeter, Charles Beromeo,Jackstell, Ralf,Beller, Matthias
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p. 1329 - 1334
(2016/04/20)
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- Hydrogenation of Aliphatic and Aromatic Nitriles Using a Defined Ruthenium PNP Pincer Catalyst
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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
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supporting information
p. 5944 - 5948
(2015/09/22)
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- Conversion of alcohols to enantiopure amines through dual-enzyme hydrogen-borrowing cascades
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α-Chiral amines are key intermediates for the synthesis of a plethora of chemical compounds at industrial scale. We present a biocatalytic hydrogen-borrowing amination of primary and secondary alcohols that allows for the efficient and environmentally benign production of enantiopure amines. The method relies on a combination of two enzymes: an alcohol dehydrogenase (from Aromatoleum sp., Lactobacillus sp., or Bacillus sp.) operating in tandem with an amine dehydrogenase (engineered from Bacillus sp.) to aminate a structurally diverse range of aromatic and aliphatic alcohols, yielding up to 96% conversion and 99% enantiomeric excess. Primary alcohols were aminated with high conversion (up to 99%). This redox self-sufficient cascade possesses high atom efficiency, sourcing nitrogen from ammonium and generating water as the sole by-product.
- Mutti, Francesco G.,Knaus, Tanja,Scrutton, Nigel S.,Breuer, Michael,Turner, Nicholas J.
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p. 1525 - 1529
(2015/10/05)
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- Amination of ω-Functionalized Aliphatic Primary Alcohols by a Biocatalytic Oxidation-Transamination Cascade
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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.
- Pickl, Mathias,Fuchs, Michael,Glueck, Silvia M.,Faber, Kurt
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p. 3121 - 3124
(2015/10/19)
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- Ruthenium/imidazolylphosphine catalysis: Hydrogenation of aliphatic and aromatic nitriles to form amines
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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
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supporting information
p. 4227 - 4231
(2014/05/06)
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- Soluble and reusable poly(norbornene) supports with high loading capacities for peptide synthesis
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Poly(norbornene) supports comprising solubilizing ethylene glycol units and multiple amino acid attachment sites have been developed for peptide synthesis. A variety of amino acids have been efficiently loaded (0.6-1.1 mmol/g) onto the support in high yields (83-98%). Several tripeptides have been synthesized in moderate-to-good overall yields (41-66%) using only 1.2 equiv of coupling reagents/amino acids, and the support could be efficiently recycled up to 3 times.
- Naganna, Nimmashetti,Madhavan, Nandita
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supporting information
p. 5870 - 5873
(2013/12/04)
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- Reaction of InCl3 with various reducing agents: InCl 3-NaBH4-mediated reduction of aromatic and aliphatic nitriles to primary amines
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While alternative methods of preparing dichloroindium hydride (HInCl 2) via the in situ reduction of InCl3 using lithium amino borohydride (LAB) were explored, generation of HInCl2 from the reduction of InCl3 by sodium borohydride (NaBH4) was also re-evaluated for comparison. The reductive capability of the InCl 3/NaBH4 system was found to be highly dependent on the solvent used. Investigation by 11B NMR spectroscopic analyses indicated that the reaction of InCl3 with NaBH4 in THF generates HInCl2 along with borane-tetrahydrofuran (BH 3?THF) in situ. Nitriles underwent reduction to primary amines under optimized conditions at 25 °C using 1 equiv of anhydrous InCl 3 with 3 equiv of NaBH4 in THF. A variety of aromatic, heteroaromatic, and aliphatic nitriles were reduced to their corresponding primary amine in 70-99% isolated yields. Alkyl halide and nitrile functional groups were reduced in tandem by utilizing the reductive capabilities of both HInCl2 and BH3?THF in a one-pot reaction. Finally, the selective reduction of the carbon bromine bond in the presence of nitriles was achieved by generating HInCl2 via the reduction InCl3 with NaBH4 in CH3CN or with lithium dimethylaminoborohydride (MeLAB) in THF.
- Saavedra, Jaime Z.,Resendez, Angel,Rovira, Alexander,Eagon, Scott,Haddenham, Dustin,Singaram, Bakthan
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experimental part
p. 221 - 228
(2012/02/05)
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- Spiroborate catalyzed reductions with N,N-diethylaniline borane
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Reduction of esters, amides, and ketones by N,N-diethylaniline borane is accelerated by catalysts derived from spiroborate complexes. Esters are reduced at ambient temperature in less than 4 h with this amine borane and 5 mol % spiroborate 6. Functional group selectivity shows ketone and tertiary amide reduction is faster than ester or nitrile reduction.
- Coleridge, Brian M.,Angert, Thomas P.,Marks, Lucas R.,Hamilton, Patrick N.,Sutton, Christopher P.,Matos, Karl,Burkhardt, Elizabeth R.
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supporting information; experimental part
p. 5973 - 5976
(2010/11/21)
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- Triggered self-assembly of simple dynamic covalent surfactants
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(Figure Presented) A prototype surfactant system was developed with the unique feature that it can be switched between an aggregated, amphiphilic state and a nonaggregated, nonamphiphilic state using external stimuli. This switchable surfactant system uses the reversible formation of a dynamic covalent bond for pH- and temperature-triggered on/off self-assembly of micellar aggregates by reversible displacement of the equilibrium between nonamphiphilic building blocks and their amphiphilic counterparts. The potential for application in controlled-release systems is shown by reversible uptake and release of an organic dye in aqueous media.
- Minkenberg, Christophe B.,Florusse, Louw,Eelkema, Rienk,Koper, Ger J. M.,Van Esch, Jan H.
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supporting information; scheme or table
p. 11274 - 11275
(2011/03/19)
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- BORANE ETHER COMPLEXES
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The present invention relates to new borane complexes with substituted tetrahydrofuran ethers and a method of using new borane complexes with substituted tetrahydrofuran ethers for organic reactions.
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Page/Page column 16
(2008/06/13)
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- Salt suitable for an acid generator and a chemically amplified positive resist composition containing the same
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The present invention provides a salt represented by the formula (I): wherein P1, P2 and P3 each independently represent a C1-C30 alkyl group which may be substituted with at least one selected from a hydroxyl group, a C3-C12 cyclic hydrocarbon group and a C1-C12 alkoxy group, or a C3-C30 cyclic hydrocarbon group which may be substituted with at least one selected from a hydroxyl group and a C1-C12 alkoxy group, provided that all of P1, P2 and P3 are not simultaneously phenyl groups which may be substituted, Q1 and Q2 each independently represent a fluorine atom or a C1-C6 perfluoroalkyl group, and R represents a group represented by the formula: wherein A1 represents —OH or —Y1—OH, n represents an integer of 1 to 9, and Y1 represents a divalent C1-C6 saturated aliphatic hydrocarbon group; a group represented by the formula: wherein ring X1 represents a C3-C30 monocyclic or polycyclic hydrocarbon group in which one —CH2— group is substituted with —CO—, and at least one hydrogen atom in the monocyclic or polycyclic hydrocarbon group may be substituted with a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C4 perfluoroalkyl group, a C1-C6 hydroxyalkyl group, a hydroxyl group or a cyano group; a group represented by the formula: wherein ring X2 represents a C3-C30 monocyclic or polycyclic hydrocarbon group in which a hydrogen atom of one —CH2— group is substituted with a hydroxyl group, and at least one hydrogen atom in the monocyclic or polycyclic hydrocarbon group may be substituted with a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C4 perfluoroalkyl group, a C1-C6 hydroxyalkyl group, a hydroxyl group or a cyano group; a group represented by the formula: wherein ring X3 represents a C3-C30 monocyclic or polycyclic hydrocarbon group in which one —CH2— group is substituted with —COO—, and at least one hydrogen atom in the monocyclic or polycyclic hydrocarbon group may be substituted with a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C4 perfluoroalkyl group, a C1-C6 hydroxyalkyl group, a hydroxyl group or a cyano group, and m represents an integer of 0 to 12; or a group represented by the formula: wherein ring X4 represents a C6-C30 polycyclic hydrocarbon group having tricycle or more, and at least one hydrogen atom in the polycyclic hydrocarbon group may be substituted with a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C4 perfluoroalkyl group, a C1-C6 hydroxyalkyl group or a cyano group, and l represents an integer of 1 to 12. The present invention further provides a chemically amplified resist composition comprising the salt represented by the above-mentioned formula (I).
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- Base induced carbon-nitrogen (C=N) double bond migration in Schiff bases
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Various Schiff bases have been prepared to study base induced carbon-nitrogen double bond migrations. Schiff bases derived from aliphatic aldehydes display highest selectivity. Hydrolysis of the resulting rearranged Schiff base provides an entry to make amines from aldehydes. The reaction has possible practical application.
- Gangadasu,Narender,China Raju,Jayathirtha Rao
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p. 2598 - 2600
(2007/10/03)
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- Non-metallocene compounds, method for the production thereof and use of the same for the polymerisation of olefins
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The invention relates to a method for producing special transition metal compounds, to novel transition metal compounds and to the use of the same for the polymerisation of olefins.
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- Polymer supported palladium (II) complexes as hydrogenation catalysts
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Dihydrogen reduction of aliphatic and aromatic nitrocompounds, alkenes, alkynes, nitriles and Schiff bases to their corresponding saturated products is efficiently carried out using the soluble and polymer anchored palladium (II) complexes. The immobilization of the palladium (II) complexes in the polymer matrix slightly decreased the catalytic activities on the basis of metal content but improved the thermal and chemical stabilities and product selectivities relative to those of the corresponding homogeneous ones. The soluble catalyst has the propensity to decompose under high pressure, high temperature conditions but the immobilized ones can be used repeatedly and can be stored for long periods without any appreciable loss of catalytic activity. XPS study indicates the presence of palladium (II) in the fresh and used catalyst and a plausible reaction mechanism has been suggested on the basis of experimental findings.
- Mukherjee, Debkumar
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p. 346 - 352
(2007/10/03)
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- 2-aminopyridine derivatives and combinatorial libraries thereof
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The present invention relates to novel 2-aminopyridine derivative compounds of the following formula: wherein R1to R5have the meanings provided herein. The invention further relates to combinatorial libraries containing two or more such compounds, as well as methods of preparing 2-aminopyridine derivative compounds.
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- Mild and efficient reduction of azides to amines: Synthesis of fused [2,1-b]quinazolinones
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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.
- Kamal, Ahmed,Ramana, K.Venkata,Ankati, Hari Babu,Ramana, A.Venkata
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p. 6861 - 6863
(2007/10/03)
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- A facile reduction of azides to the corresponding amines with Sm/NiCl2·6H2O system
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Azides can be easily reduced to the corresponding amines with Sm/NiCl2·6H2O in excellent yields under mild and neutral conditions.
- Wu, Huayue,Chen, Rener,Zhang, Yongmin
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p. 189 - 193
(2007/10/03)
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- Reduction of oximes with sodium borohydride - Copper (II) sulfate in methanol
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Reduction of aldoximes and ketoximes with sodium borohydride in methanol reflux results in corresponding primary and secondary amines in good yields.
- Rao, H. Surya Prakash,Bharathi
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p. 1072 - 1074
(2007/10/03)
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- A novel method for the chemoselective reduction of azides to amines with a Sm/CoCl2·6H2O system
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Azides can be easily reduced to the corresponding amines with Sm/CoCl2·6H2O in excellent yields under mild and neutral conditions.
- Wu, Huayue,Chen, Rener,Zhang, Yongmin
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p. 248 - 249
(2007/10/03)
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- Reductions with lithium in low molecular weight amines and ethylenediamine
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Reductions of several types of compounds with lithium and ethylenediamine using low molecular weight amines as solvent are described. In all cases 1 mol of ethylenediamine or N,N'-dimethylethylenediamine per gram-atom of lithium was used. In some cases it was beneficial to add an alcohol as a proton donor. These reaction conditions were applied to the debenzylation of N-benzylamide and lactams which are refractory to hydrogenolysis with hydrogen and a catalyst. N-Benzylpilolactam 2, synthesized from pilocarpine hydrochloride in refluxing benzylamine, was debenzylated in good yield using 10 gram-atoms of lithium per mole (10 Li/mol) of 2 in n-propylamine. The debenzylation of N-benzyl-N-methyldecanoic acid amide, 4 (6 Li/mol), in t-butylamine/N,N'-dimethylethylenediamine gave N-methyldecanoic acid amide 6 in 70% yield. Alternatively, reduction of 4 (7 Li/mol) in t-butanol/n-propylamine/ethylenediamine gave n-decanal 12 in 36% yield. Using the same conditions, thioanisole, 1-adamantane-p-toluenesulfonamide, and 1-adamantane methyl p-toluenesulfonate were reduced with 3, 7, and 7.2 Li/mol of compound to give thiophenol (74%), adamantamine (91%), and 1-adamantane methanol (75%), respectively. In this solvent system naphthalene and 3-methyl-2-cyclohexene-1-one were reduced to isotetralin (74%) and 3-methyl cyclohexanone (quantitative) with 5 and 2.2 Li/mol of starting compound, respectively. Oximes and O-methyloximes were reduced to their corresponding amines using 5 and 8 Li/mol of compound, respectively. Anisole was also reduced to 1-methoxy-1,4-cyclohexadiene with 2.5 Li/mol of anisole. Undecanenitrile was reduced to undecylamine with 8.6 Li/mol. Additionally, a base-catalyzed formation of imidazolines from a nitrile and ethylenediamine was also explored.
- Garst,Dolby,Esfandiari,Fedoruk,Chamberlain,Avey
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p. 7098 - 7104
(2007/10/03)
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- Catalysis of ester aminolysis by cyclodextrins. The reaction of alkylamines with p-nitrophenyl alkanoates
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The effects of four cyclodextrins (α-CD, β-CD, hydroxypropyl-β-CD, and γ-CD) on the aminolysis of p-nitrophenyl alkanoates (acetate to heptanoate) by primary amines (n-propyl to n-octyl, isobutyl, isopentyl, cyclopentyl, cyclohexyl, benzyl) in aqueous solution have been investigated. Rate constants for amine attack on the free and CD-bound esters (k(N) and k(cN)) have ratios (k(cN)/k(N)) varying from 0.08 (retardation) to 180 (catalysis). For the kinetically equivalent process of free ester reacting with CD-bound amine (k(Nc)), the ratios k(Nc)/k(N) vary from 0.2 to 28. Either way, there is evidence of catalysis in some cases and retardation in others. Changes in reactivity parameters with structure indicate more than one mode of transition state binding to the CDs. Short esters react with short alkylamines by attack of free amine on the ester bound by its aryl group, but for longer amines, free ester reacts with CD-bound amine. Reaction of long esters with long amines, which is catalyzed by β-CD and γ-CD, involves inclusion of the alkylamino group and possibly the ester acyl group. The larger cavity of γ-CD may allow the inclusion of the ester aryl group, as well as the alkylamino group, in the transition state. Reaction between an ester bound to the CD by its acyl group and free amine appears not to be important.
- Gadosy,Boyd,Tee
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p. 6879 - 6889
(2007/10/03)
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- Molecular addition compounds. 15. Synthesis, hydroboration, and reduction studies of new, highly reactive tert-butyldialkylamine-borane adducts
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Two series of tert-butyldialkylamines have been prepared and examined for borane complexation. The complexing ability of each amine in the two series examined decreases in the order shown. First series: t- BuN(CH2CH2)2O 1a > t-BuNEt2 1b > t-BuNPr(n)21c > t-BuN(CH2CH2OMe)2 1d >> t-BuNBu(i)2 1e. Second series: t-BuNBu(i)Me 2a > t-BuNPr(i)Me 2b > t- BuNBu(i)Et 2c > t-BuNBu(i)Pr(n) 2d >>t-BuNPr(i)Et 2e. The reactivity of the corresponding borane adducts toward 1-octene increases in the reverse order. The following amines form highly reactive liquid borane adducts hydroborating 1-octene in tetrahydrofuran at room temperature in less than 1 h: t- BuN(CH2CH2OMe)2, t-BuNBu(i)Et, and t-BuNPr(i)Me. The limit of borane complexation among the amines examined is reached for t-BuNBu(i)2 exchanging borane neither with BMS nor with BH3-THF. Among the various borane adducts prepared, the more promising borane adducts, t-Bu(CH3OCH2CH2)2N-BH3 (7), t-BuMePr(i)N-BH3 (8), and t-BuEtBu(i)N-BH3 (9), were selected for complete hydroboration and reduction studies. Hydroboration studies with the new, highly reactive trialkylamine-borane adducts 7-9 and representative olefins, such as 1-hexene, styrene, β-pinene, cyclopentene, norbornene, cyclohexene, 2-methyl-2-butene, α-pinene, and 2,3-dimethyl-2-butene, in tetrahydrofuran, dioxane, tert-butyl methyl ether, n-pentane, and dichloromethane, at room temperature (22 ± 3°C) were carried out. The reactions are faster in dioxane, requiring 1-2 h for the hydroboration of simple, unhindered olefins to the trialkylborane stage. Moderately hindered olefins, such as cyclohexene and 2-methyl-2-butene, give the corresponding dialkylboranes rapidly, with further slow hydroboration. However, the more hindered olefins, α-pinene and 2,3-dimethyl-2-butene, give stable monoalkylboranes very rapidly, with further hydroboration proceeding relatively slowly. The hydroborations can also be carried out conveniently in other solvents, such as THF, tert-butyl methyl ether, and n-pentane. A significant rate retardation is observed in dichloromethane. Regioselectivity studies of 1-hexene and styrene using these amine-borane adducts show selectivities similar to that of BH3-THF. The rates and stoichiometry of the reaction of t-BuMePr(i)N-BH3 in tetrahydrofuran with selected organic compounds containing representative functional groups were also examined at room temperature. The reductions of esters, amides, and nitriles, which exhibit a sluggish reaction at room temperature, proceed readily under reflux conditions in tetrahydrofuran and dioxane and without solvent (at 85-90°C). The carrier amines can be recovered by simple acid-base manipulations in good yield and readily recycled to make the borane adducts.
- Brown, Herbert C.,Kanth, Josyula V. B.,Dalvi, Pramod V.,Zaidlewicz, Marek
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p. 6263 - 6274
(2007/10/03)
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- N-carboalkoxy-2-nitrobenzenesulfonamides: A practical preparation of N- Boc-, N-Alloc-, and N-Cbz-protected primary amines
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N-Carboalkoxy-2-nitrobenzenesulfonamides, readily prepared by acylation of 2-nitrobenzenesulfonamide (o-NsNH2), can be alkylated by either conventional or Mitsunobu protocols. Since the o-nosyl group can be deprotected under mild conditions, a variety of N-carboalkoxy derivatives of primary amines may be prepared in excellent yields from the corresponding alcohols and/or halides. In addition, allyloxycarbonyl (Alloc), t- butoxycarbonyl (t-Boc), and benzyloxycarbonyl (Cbz) groups can be deprotected in the presence of the o-nosyl group, allowing the resultant N-alkylated 2- nitrobenzenesulfonamides to be used for further preparation of secondary amines.
- Fukuyama, Tohru,Cheung, Mui,Kan, Toshiyuki
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p. 1301 - 1303
(2007/10/03)
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- Lithium and amine dissolving metal reduction
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The invention is directed to a process for reducing or reductively cleaving an organic compound susceptible to dissolving metal reduction comprising exposing the organic compound to a solution of lithium in a polyamine including at least two amino groups, selected from the group consisting of primary and secondary amino groups and mixtures thereof, e.g. ethylenediamine and R--NH2, optionally containing a lower alkyl alcohol, wherein R is chosen from the group consisting of ethyl, propyl, and butyl, including all straight and branched chain isomers thereof, for a time sufficient to effect reduction.
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- Iodotrimethylsilane: A mild and efficient reagent for the reduction of azides to amines
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Chlorotrimethylsilane - sodium iodide reagent (in situ generation of iodotrimethylsilane) in acetonitrile reduces alkyl and aryl/aroyl azides to the corresponding amines/amides in excellent yields under neutral and mild conditions.
- Kamal, Ahmed,Rao, N. Venugopal,Laxman
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p. 6945 - 6948
(2007/10/03)
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- Facile reduction of azides to the corresponding amines with metallic samarium and catalytic amount of iodine
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Samarium and a catalytic amount of iodine in methanol reduce alkyl and aryl azides to the corresponding amines, and aroyl, sulfonyl azides to the corresponding amides in good yields under neutral and mild condition.
- Huang, You,Zhang, Yongmin,Wang, Yulu
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p. 1065 - 1066
(2007/10/03)
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- Thermodynamic and nuclear magnetic resonance study of the reactions of α- and β-cyclodextrin with acids, aliphatic amines, and cyclic alcohols
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Titration calorimetry was used to determine equilibrium constants and standard molar enthalpy, Gibbs energy, and entropy changes for the reactions of a series of acids, amines, and cyclic alcohols with α- and β-cyclodextrin. The results have been examined in terms of structural features in the ligands such as the number of alkyl groups, the charge number, the presence of a double bond, branching, and the presence of methyl and methoxy groups. The values of thermodynamic quantities, in particular the standard molar Gibbs energy, correlate well with the structural features in the ligands. These structural correlations can be used for the estimation of thermodynamic quantities for related reactions. Enthalpy-entropy compensation is evident when the individual classes of substances studied herein are considered, but does not hold when these various classes of ligands are considered collectively. The NMR results indicate that the mode of accommodation of the acids and amines in the α-cyclodextrin cavity is very similar, but that the 1-methyl groups in 1-methylhexylamine and in 1-methylheptylamine and the N-methyl group in N-methylhexylamine lie outside the α-cyclodextrin cavity. This latter finding is consistent with the calorimetric results. Many of the thermodynamic and NMR results can be qualitatively understood in terms of van der Waals forces and hydrophobic effects.
- Rekharsky, Mikhail V.,Mayhew, Martin P.,Goldberg, Robert N.,Ross, Philip D.,Yamashoji, Yuko,Inoue, Yoshihisa
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- Reduction of azides to amines with SmI2 OR Cp2TiCl2-Sm system
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Azides can be rapidly reduced to corresponding amines with SmI2 (method A) or Cp2TiCl2-Sm system (method B) in good yields under mild conditions.
- Huang, You,Zhang, Yongmin,Wang, Yulu
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p. 2911 - 2915
(2007/10/03)
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- Efficient Reduction of Azides with Samarium Diiodide
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Reduction of alkyl, aryl and aroyl azides to the parent primary amines or amides, respectively, occurs in good yield upon treatment with an excess of SmI2 in THF at room temperature.A radical mechanism is proposed.
- Goulaouic-Dubois, Catherine,Hesse, Manfred
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p. 7427 - 7430
(2007/10/02)
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- Chromium-Pillared Clay as a Catalyst for Benzylic Oxidation and Oxidative Deprotection of Benzyl Ethers and Benzylamines: A Simple and Convenient Procedure
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A mild and efficient method for benzylic oxidation of arylmethylenes to the corresponding carbonyl compounds in good yields is described using a catalytic amount of chromium-pillared montmorillonite and equimolar quantities of tert-butyl hydroperoxide.The method is very selective toward monocarbonyl compounds of the substrates prone to form dicarbonyl compounds.The present heterogeneous catalyst is inert toward the branched hydrocarbone and has been put to practice to obtain p-isobutylacetophenone selectively from p-isobutylethylbenzene.Further, the method is extended successfully to the oxidative debenzylation reactions for the first time.A striking feature of the oxidative deprotection with the present method is the deprotection of a benzyl group from the substrates having any alkyne moiety.
- Choudary, Boyapati M.,Prasad, Annavajhula Durga,Bhuma, Vendantam,Swapna, Vinukonda
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p. 5841 - 5844
(2007/10/02)
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- Chromium pillared clay catalysed allylic oxidation and oxidative deprotection of allyl ethers and amines : A simple and convenient procedure
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An efficient method for allylic oxidation of cyclic and acyclic alkenes to the corresponding α,β-unsaturated carbonyl compounds in good yields was described using catalytic amounts of chromiapillared montmorillonite and equimolar quantities of tert-butyl hydroperoxide. This is also a convenient method for selective oxidative deprotection of allyl ethers and amines using same system. Incidentally this is the first heterogeneous system for the allylic oxidation as well as oxidative deprotection.
- Choudary, Boyapati M.,Prasad, Annavajhula Durga,Swapna, Vinukonda,Valli, Velaga L. K.,Bhuma, Vedantam
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p. 953 - 962
(2007/10/02)
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- Stereospecific synthesis of Z olefins bearing an ω-azido group.
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Ylides derived from ω-azidoalkyltriphenylphosphonium salts were generated at low temperature.They are stable at -80 deg C for several hours and react smoothly and stereospecifically with typical aldehydes to form Z-ω-azido olefins which are the precursors of ω-unsaturated primary and secondary amines.
- Chhen, A.,Vaultier, M.,Carrie, R.
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p. 4953 - 4956
(2007/10/02)
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- THE DEPROTECTION OF METHYL CARBAMATES BY SODIUM HYDROGEN TELLURIDE
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Methyl carbamates, prepared by reacting primary and seconadry amines with chlorocarbonate, react smoothly with sodium hydrogen telluride in DMF and regenerate the amines in moderate yields.
- Zhou, Xun-Jun,Huang, Zhi-Zhen
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p. 1347 - 1350
(2007/10/02)
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- 3-amino-5-methyl-1H-pyrazole-4-carboxylic acids and esters thereof as anticonvulsants, muscle relaxants and anxiolytics
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A novel method of controlling epilepsy, muscle tension, muscular spasticity, and anxiety in living animal bodies by administering compounds of the formula: STR1 wherein: R1 is hydrogen, loweralkyl or a pharmaceutically acceptable cation; R2 and R3, same or different, are hydrogen, loweralkyl, aryl, cycloalkyl, loweralkenyl, 1-adamantyl, heterocyclicaminoalkyl, diloweralkylaminoloweralkyl, or R2 with R3 and adjacent nitrogen may form a heterocyclic ring structure; and the pharmaceutical acceptable acid salts, and tautomeric isomers thereof; and novel pharmaceutical compositions therefor are disclosed.
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- ALKALINE EARTH METAL MEDIATED REDUCTION OF AZIDES TO AMINES
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A mild and facile method for the reduction of alkyl and aryl azides to the corresponding amines using alkaline earth metals is described.
- Maiti, Samarendra N.,Spevak, Paul,Reddy, A. V. Narender
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p. 1201 - 1206
(2007/10/02)
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