- N?N Bond Formation Using an Iodonitrene as an Umpolung of Ammonia: Straightforward and Chemoselective Synthesis of Hydrazinium Salts
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The formation of hydrazinium salts by N?N bond formation has typically involved the use of hazardous and difficult to handle reagents. Here, mild and operationally simple conditions for the synthesis of hydrazinium salts are reported. Electrophilic nitrogen transfer to the nitrogen atom of tertiary amines is achieved using iodosylbenzene as oxidant and ammonium carbamate as the N-source. The resulting process is highly chemoselective and tolerant to other functional groups. A wide scope is reported, including examples with bioactive molecules. Insights on the structure of hydrazinium salts were provided by X-ray analysis. (Figure presented.).
- Tota, Arianna,Colella, Marco,Carlucci, Claudia,Aramini, Andrea,Clarkson, Guy,Degennaro, Leonardo,Bull, James A.,Luisi, Renzo
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supporting information
p. 194 - 199
(2020/10/28)
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- Electrochemical deoxygenation of aromatic amides and sulfoxides
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The electrochemical deoxygenation of a broad range of aromatic amides was achieved under mild conditions on lead cathodes. Under the optimized reaction conditions, acetal, thienyl, and ether moieties are tolerated. Furthermore, the reduction protocol can be applied to aromatic and aliphatic sulfoxides to obtain the corresponding sulfides. For both aromatic amides and sulfoxides, the deoxygenation reaction ensues without the use of expensive catalysts or hazardous reducing agents. Owing to the high selectivity of the process, simple extraction is sufficient to isolate the product from the substrate. The straightforward purification protocol, the coformation of water, and the use of electric current instead of reducing agents render our method environmentally friendly and economically beneficial. Copyright
- Edinger, Carolin,Waldvogel, Siegfried R.
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supporting information
p. 5144 - 5148
(2014/10/15)
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- A practical regioselective synthesis of alkylthio- or arylthioindoles without the use of smelly compounds such as thiols
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A convenient method for the synthesis of 3-methylthioindoles has been established which does not use smelly compounds such as thiol derivatives. The method, which introduces an alkyl- or arylthio-group into the C3-position of the indole skeleton, was extended to the direct introduction of a methylthio or bromo group at the C2-position using 3-methylthioindoles. No dimerization occurred, and the reaction mechanism was confirmed. The products have the partial structure of potent anti-methicillin-resistant Staphylococcus aureus (anti-MRSA) bromomethylthioindoles (MC 5-8) isolated from marine algae. Furthermore, this reaction could be applied to the synthesis of 3,3-diindolyl thioether which is a core structure of Echinosulfone A.
- Hamashima, Toshihiko,Mori, Yoshiaki,Sawada, Kazunori,Kasahara, Yuko,Murayama, Daisuke,Kamei, Yuto,Okuno, Hiroaki,Yokoyama, Yuusaku,Suzuki, Hideharu
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p. 292 - 303
(2013/05/08)
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- Cobalt carbonyl-based catalyst for hydrosilylation of carboxamides
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The cobalt carbonyl [Co2(CO)8] complex is employed as a useful catalyst for the reduction of tertiary amides to the corresponding tertiary amines using 1,1,3,3-tetramethyldisiloxane (TMDS) and poly(methylhydrosiloxane) (PMHS) as silane reagents under thermal (100 °C) or photo-assisted conditions (UV, 350 nm at room temperature). Of particular interest, a low catalytic amount (0.5 mol%) of [Co2(CO)8] is used to perform the reaction with 2.2 equiv. of PMHS at 100 °C for 3 h. This reaction is the first example of a cobalt-catalyzed hydrosilylation of amides. Copyright
- Dombray, Thomas,Helleu, Camille,Darcel, Christophe,Sortais, Jean-Baptiste
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supporting information
p. 3358 - 3362
(2013/12/04)
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- Phosphane-pyridine iron complexes: Synthesis, characterization and application in reductive amination through the hydrosilylation reaction
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A series of 6 cyclopentadienyl phosphanyl-pyridine piano-stool iron complexes was prepared in good yields, characterized, and studied in the catalytic reductive amination of benzaldehyde derivatives through hydrosilylation reactions by using polymethylhydrosiloxane as the hydrosilane source and in dimethylcarbonate as the solvent at 40 °C. Single-crystal X-ray structural analyses were performed for all the complexes. A series of 6 cyclopentadienyl phosphanyl-pyridine piano-stool iron complexes was prepared, characterized, and studied in the catalytic reductive amination of benzaldehyde derivatives in dimethylcarbonate through hydrosilylation reactions by using polymethylhydrosiloxane as the hydrosilane source. Copyright
- Jaafar, Hassen,Li, Haoquan,Misal Castro, Luis C.,Zheng, Jianxia,Roisnel, Thierry,Dorcet, Vincent,Sortais, Jean-Baptiste,Darcel, Christophe
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experimental part
p. 3546 - 3550
(2012/10/18)
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- Reductive amination of carbonyl compounds over silica supported palladium exchanged molybdophosphoric acid catalysts
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Palladium exchanged molybdophosphoric acid supported on silica is reported as a highly effective catalyst for direct reductive amination of carbonyl compounds. The catalysts are characterized by X-ray diffraction and FT-infrared spectroscopy. The characterization results support the existence of Keggin ion of heteropoly molybdate on silica. The catalyst is facile, water tolerable and environmentally benign for reductive amination. A variety of secondary and tertiary amines can be synthesized over this catalyst in excellent yields under mild reaction conditions. A plausible reaction mechanism is proposed for the reductive amination of carbonyl compounds over this catalyst.
- Srivani,Prasad, P. S. Sai,Lingaiah
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experimental part
p. 389 - 396
(2012/06/18)
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- Borrowing hydrogen in water and ionic liquids: Iridium-catalyzed alkylation of amines with alcohols
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The use of [Cp*IrI2]2 as an efficient catalyst for the alkylation of amines by alcohols in either water or ionic liquid is described. Primary amines are converted into secondary amines, and secondary amines into tertiary amines in the absence of base, and the chemistry has been applied to the synthesis of the analgesic fentanyl. The conversion of primary amines into N-heterocycles by the reaction with diols is also described, along with the N-alkylation of sulfonamides.
- Saidi, Ourida,Blacker, A. John,Lamb, Gareth W.,Marsden, Stephen P.,Taylor, James E.,Williams, Jonathan M. J.
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supporting information; experimental part
p. 1046 - 1049
(2011/03/20)
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- Iron-catalyzed, hydrogen-mediated reductive cyclization of 1,6-enynes and diynes: Evidence for bis(imino)pyridine ligand participation
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(Chemical Equation Presented) The bis(imino)pyridine iron dinitrogen complex (iPrPDI)Fe(N2)2 catalyzes the hydrogen-mediated reductive cyclization of enynes and diynes with turnover frequencies comparable to those of established precious metal catalysts. Amino, oxygenated, and carbon-based substrates are readily cyclized to the corresponding hetero- and carbocycles with 5 mol % iron and 4 atm H2 at 23°C. Stoichiometric reactions between selected substrates and the iron compound under a N2 atmosphere established transfer dehydrogenation from an isopropyl aryl substituent to either the enyne or diyne substrate. In situ monitoring of the catalytic reaction by 1H NMR spectroscopy coupled with deuterium labeling experiments established rapid cyclization followed by turnoverlimiting hydrogenation. Copyright
- Sylvester, Kevin T.,Chirik, Paul J.
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supporting information; experimental part
p. 8772 - 8774
(2009/12/04)
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- Ruthenium-catalyzed /V-alkylation of amines and sulfonamides using borrowing hydrogen methodology
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The alkylation of amines by alcohols has been achieved using 0.5 mol percent [Ru(p-cymene)CI2]2 with the bidentate phosphines dppf or DPEphos as the catalyst. Primary amines have been converted into secondary amines, and secondary amines into tertiary amines, including the syntheses of Piribedil, Tripelennamine, and Chlorpheniramine. A/-Heterocyclization reactions of primary amines are reported, as well as alkylation reactions of primary sulfonamides. Secondary alcohols requiremore forcing conditions than primary alcohols but are still effective a lkylating agents in the presence of this catalyst.
- Hamid, M. Haniti S. A.,Allen, C. Liana,Lamb, Gareth W.,Maxwell, Aoife C.,Maytum, Hannah C.,et al.
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supporting information; experimental part
p. 1766 - 1774
(2009/07/25)
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- Reductive amination with 5-ethyl-2-methylpyridine borane
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We report a new amine borane, 5-ethyl-2-methylpyridine borane complex (PEMB) useful for reductive aminations of ketones and aldehydes in methanol or neat. Two of the three hydrides on PEMB are effectively utilized maximizing the economy of the reagent.
- Burkhardt, Elizabeth R.,Coleridge, Brian M.
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p. 5152 - 5155
(2008/12/20)
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- Ruthenium-catalysed synthesis of tertiary amines from alcohols
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Secondary amines have been converted into tertiary amines by reactions with primary alcohols. A catalytic system of [Ru(cymene)Cl2]2 with dppf has been shown to be effective for this transformation for a range of primary alcohols and secondary amines. The methodology has been applied to the one pot synthesis of Piribedil and other piperazine and morpholine-containing products.
- Hamid, M. Haniti S.A.,Williams, Jonathan M.J.
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p. 8263 - 8265
(2008/03/14)
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- One-pot reductive amination of aldehydes and ketones with α-picoline-borane in methanol, in water, and in neat conditions
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A one-pot reductive amination of aldehydes and ketones with amines using α-picoline-borane as a reducing agent is described. The reaction has been carried out in MeOH, in H2O, and in neat conditions in the presence of small amounts of AcOH. This is a highly efficient and mild procedure that is applicable for a wide variety of substrates. In particular, this is the first successful demonstration that this type of reaction can be carried out in water and in neat conditions.
- Sato, Shinya,Sakamoto, Takeshi,Miyazawa, Etsuko,Kikugawa, Yasuo
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p. 7899 - 7906
(2007/10/03)
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- Hydroamination of carbonyl compounds with oximes
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N-alkyl(cycloalkyl)benzylamines, p-fluorobenzylamines, (1-phenylethyl) amines, [1-(p-fluorophenyl)ethyl]amines were synthesized by hydroamination of aldehydes and ketones with oximes.
- Tarasevich,Kozlov
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p. 379 - 383
(2007/10/03)
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- Catalytic process
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The present invention relates to methods for the reductive amination of a carbonyl-containing compound. R1R2CO where R1and R2are either H, alkyl, aryl or heterocyclic etc with an amine NHR3R4/su
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- Reductive amination process using a homogeneous iridium catalyst
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The present invention relates to methods for the reductive amination of a carbonyl-containing compound. R1R2CO where R1 and R2 are either H, alkyl, aryl or heterocyclic etc with an amine NHR3R4/
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- Gas-phase selective N-alkylation of amines with alcohols over γ- alumina
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Gas-phase conditions were successfully used for fine chemistry, in the N-alkylation of amines with alcohols as alkylating agents and γ-alumina as a catalyst. The method is also suitable for chiral compounds.
- Valot, Frederic,Fache, Fabienne,Jacquot, Roland,Spagnol, Michel,Lemaire, Marc
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p. 3689 - 3592
(2007/10/03)
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- Effect of branching in alkylgroups of tertiary amines on their performance as catalysts in the high pressure promoted Bylis-Hillman reaction
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Receptors 1 were tested as catalysts for the high pressure promoted Baylis-Hillman reaction. Surprisingly most of the compounds were found to be catalytically inactive. With model compounds (simple acyclic tertiary amines) it could be shown that tertiary amines with branches at their α-carbon atoms show a remarkable decreased activity. It is proposed that the branches prevent attack of the lone pair of the amine on the double bond of the alkene. This explains why only receptors without this feature are catalytically active.
- Schuurman,Linden,Grimbergen,Nolte,Scheeren
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p. 8307 - 8314
(2007/10/03)
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- ESTERS OF (TRIARYLPHOSPHORANYLIDENE)CARBAMIC ACID FOR EFFECTING DIURESIS
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This disclosure describes novel esters of (triarylphosphoranylidene) carbamic acid which are useful as diuretic agents.
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