- One-pot synthesis of aldoximes from alkenes: Via Rh-catalysed hydroformylation in an aqueous solvent system
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Aldoxime synthesis directly starting from alkenes was successfully achieved through the combination of hydroformylation and subsequent condensation of the aldehyde intermediate with aqueous hydroxylamine in a one-pot process. The metal complex Rh(acac)(CO)2 and the water-soluble ligand sulfoxantphos were used as the catalyst system, providing high regioselectivities in the initial hydroformylation. A mixture of water and 1-butanol was used as an environmentally benign solvent system, ensuring sufficient contact of the aqueous catalyst phase and the organic substrate phase. The reaction conditions were systematically optimised by Design of Experiments (DoE) using 1-octene as a model substrate. A yield of 85% of the desired linear, terminal aldoxime ((E/Z)-nonanal oxime) at 95% regioselectivity was achieved. Other terminal alkenes were also converted successfully under the optimised conditions to the corresponding linear aldoximes, including renewable substrates. Differences of the reaction rate have been investigated by recording the gas consumption, whereby turnover frequencies (TOFs) >2000 h-1 were observed for 4-vinylcyclohexene and styrene, respectively. The high potential of aldoximes as platform intermediates was shown by their subsequent transformation into the corresponding linear nitriles using aldoxime dehydratases as biocatalysts. The overall reaction sequence thus allows for a straightforward synthesis of linear nitriles from alkenes with water being the only by-product, which formally represents an anti-Markovnikov hydrocyanation of readily available 1-alkenes.
- Gr?ger, H.,Guntermann, A.,Hinzmann, A.,Jolmes, T.,Panke, D.,Plass, C.,R?sler, J.,Seidensticker, T.,Terhorst, M.,Vogt, D.,Vorholt, A. J.
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supporting information
p. 7974 - 7982
(2020/11/30)
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- Method for continuous preparation of nitriles in a pipelined reactor (by machine translation)
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The method comprises the following steps that a tin catalyst is coated on the inner wall of the pipeline reactor; and the method comprises the following steps: coating a tin catalyst on the inner wall of the pipeline reactor. The amide solution and the catalytic auxiliary agent are mixed and then sent to a pipeline reactor, and the amide is dehydrated to generate nitrile at the reaction pressure of 0.1 - 2.0 mpa and 100 - 200 °C reaction temperature. The resulting reaction product was separated to give the crude product of the nitrile to which the amide corresponded. In the pipeline reactor, the corresponding nitrile is continuously prepared under the action of the tin catalyst, a dehydrating agent is not needed, byproducts only are water, and three wastes are reduced. (by machine translation)
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Paragraph 0036-0047; 0056; 0058
(2020/12/14)
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- Radical cyanomethylation via vinyl azide cascade-fragmentation
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Herein, a novel methodology for radical cyanomethylation is described. The process is initiated by radical addition to the vinyl azide reagent 3-azido-2-methylbut-3-en-2-ol which triggers a cascade-fragmentation mechanism driven by the loss of dinitrogen and the stabilised 2-hydroxypropyl radical, ultimately effecting cyanomethylation. Cyanomethyl groups can be efficiently introduced into a range of substrates via trapping of α-carbonyl, heterobenzylic, alkyl, sulfonyl and aryl radicals, generated from a variety of functional groups under both photoredox catalysis and non-catalytic conditions. The value of this approach is exemplified by the late-stage cyanomethylation of pharmaceuticals.
- Donald, James R.,Berrell, Sophie L.
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p. 5832 - 5836
(2019/06/17)
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- Double Dehydrogenation of Primary Amines to Nitriles by a Ruthenium Complex Featuring Pyrazole Functionality
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A ruthenium(II) complex bearing a naphthyridine-functionalized pyrazole ligand catalyzes oxidant-free and acceptorless selective double dehydrogenation of primary amines to nitriles at moderate temperature. The role of the proton-responsive entity on the ligand scaffold is demonstrated by control experiments, including the use of a N-methylated pyrazole analogue. DFT calculations reveal intricate hydride and proton transfers to achieve the overall elimination of 2 equiv of H2.
- Dutta, Indranil,Yadav, Sudhir,Sarbajna, Abir,De, Subhabrata,H?lscher, Markus,Leitner, Walter,Bera, Jitendra K.
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supporting information
p. 8662 - 8666
(2018/07/09)
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- Amino acid derived ionic liquid supported iron Schiff base catalyzed greener approach for the aerobic oxidation of amines to nitriles
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Amino acid dl-threonine derived ionic liquid was treated with salicylaldehyde to give corresponding Schiff base which subsequently is complexed with iron and used as a green catalyst for aerobic oxidation of amines under solvent-less conditions. The developed catalyst was readily synthesized, reusable, and exhibited superior catalytic activity owing to the synergistic effect of ionic liquid moiety. The developed catalyst was found to be quite stable and could be reused for several runs without any significant loss in catalytic activity.
- Varyani, Manish,Khatri, Praveen K.,Jain, Suman L.
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p. 723 - 727
(2016/02/09)
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- Structure-activity relationship studies of the lipophilic tail region of sphingosine kinase 2 inhibitors
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Sphingosine-1-phosphate (S1P) is a ubiquitous, endogenous small molecule that is synthesized by two isoforms of sphingosine kinase (SphK1 and 2). Intervention of the S1P signaling pathway has attracted significant attention because alteration of S1P levels is linked to several disease states including cancer, fibrosis, and sickle cell disease. While intense investigations have focused on developing SphK1 inhibitors, only a limited number of SphK2-selective agents have been reported. Herein, we report our investigations on the structure-activity relationship studies of the lipophilic tail region of SLR080811, a SphK2-selective inhibitor. Our studies demonstrate that the internal phenyl ring is a key structural feature that is essential in the SLR080811 scaffold. Further, we show the dependence of SphK2 activity and selectivity on alkyl tail length, suggesting a larger lipid binding pocket in SphK2 compared to SphK1.
- Congdon, Molly D.,Childress, Elizabeth S.,Patwardhan, Neeraj N.,Gumkowski, James,Morris, Emily A.,Kharel, Yugesh,Lynch, Kevin R.,Santos, Webster L.
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p. 4956 - 4960
(2015/10/28)
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- LONG CHAIN BASE SPHINGOSINE KINASE INHIBITORS
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The invention relates to inhibitors of sphingosine kinase enzymatic activity, compounds and pharmaceutical compositions that inhibit sphingosine kinase 1 and sphingosine kinase 2 (SphK1 and SphK2) enzymes and further relates to methods of treating diseases and disorders mediated by sphingosine 1 phosphate activity, comprising administering an effective amount of sphingosine kinase inhibitors.
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Paragraph 0400; 0406
(2013/08/28)
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- Radical cyanation of alkyl iodides with diethylphosphoryl cyanide
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The β-elimination of an organophosphoryl group from an iminyl radical is observed for the first time. On the basis of this finding, radical cyanation of alkyl iodides is achieved by using diethylphosphoryl cyanide. Georg Thieme Verlag Stuttgart.
- Chang, Ho Cho,Jin, Young Lee,Kim, Sunggak
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experimental part
p. 81 - 84
(2009/05/30)
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- Polycyclic aromatic compounds-mediated electrochemical reduction of alkyl mesylates
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Electrochemical reduction of alkyl mesylates was successfully carried out by using an undivided cell equipped with a Pt cathode and an Mg anode in the presence of biphenyl and t-BuOH. The reaction could proceed efficiently under mild conditions to give the corresponding alkanes in moderate to good yields. This procedure could also be applicable to chemoselective reduction of mesylates having functional groups such as epoxide, olefin, acetal, hydroxy, or cyano groups. Copyright
- Senboku, Hisanori,Takahashi, Megumi,Fukuhara, Tsuyoshi,Hara, Shoji
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p. 228 - 229
(2008/02/04)
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- Direct oxidative conversion of alcohols and amines to nitriles with molecular iodine and DIH in aq NH3
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Simple and high-yield procedures for the direct oxidative conversion of various primary alcohols, and primary, secondary, and tertiary amines to the corresponding nitriles were successfully carried out with molecular iodine in aq ammonia and 1,3-diiodo-5,5-dimethylhydantoin in aq NH3, respectively.
- Iida, Shinpei,Togo, Hideo
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p. 8274 - 8281
(2008/02/08)
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- Borrowing hydrogen: Indirect "Wittig" olefination for the formation of C-C bonds from alcohols
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The successful development of an indirect three-step domino sequence for the formation of C-C bonds from alcohol substrates is described. An iridium-catalysed dehydrogenation of alcohol 1 affords the intermediate aldehyde 2. The desired C-C bond can then be formed by a facile Wittig olefination, yielding the intermediate alkene 3. In the final step the alkene is hydrogenated to afford the indirect Wittig product, the alkane 4. The key to this process is the concept of borrowing hydrogen; hydrogen removed in the initial dehydrogenation step is simply borrowed by the iridium catalyst. Functioning as a hydrogen reservoir, the catalyst facilitates C-C bond formation before subsequently returning the borrowed hydrogen in the final step. Herein we present full details of our examination into both the substrate and reaction scope and the limitations of the catalytic cycle. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.
- Black, Phillip J.,Edwards, Michael G.,Williams, Jonathan M. J.
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p. 4367 - 4378
(2007/10/03)
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- Direct oxidative conversion of primary alcohols to nitriles using molecular iodine in ammonia water
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A simple, effective, high-yield procedure for the direct oxidative conversion of alcohols to nitriles, was successfully carried out with molecular iodine in ammonia water. Georg Thieme Verlag Stuttgart.
- Mori, Naoshi,Togo, Hideo
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p. 1456 - 1458
(2007/10/03)
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- Phosphaadamantanes as ligands for palladium catalyzed cross-coupling chemistry: Library synthesis, characterization, and screening in the Suzuki coupling of alkyl halides and tosylates containing β-hydrogens with boronic acids and alkylboranes
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A 15-member library of phosphaadamantane ligands has been prepared via P-arylation of 1,3,5,7-tetramethyl-2,4,8-trioxa-6-phosphaadamantane. Screening of this tertiary phosphine collection has allowed for the rapid determination of the most suitable ligand, specifically 1,3,5,7-tetramethyl-6-(2,4- dimethoxyphenyl)-2,4,8-trioxa-6-phosphaadamantane, for facilitating Suzuki-type couplings of alkyl halides or tosylates containing β-hydrogens with either boronic acids or alkylboranes.
- Brenstrum, Tim,Gerristma, David A.,Adjabeng, George M.,Frampton, Christopher S.,Britten, James,Robertson, Alan J.,McNulty, James,Capretta, Alfredo
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p. 7635 - 7639
(2007/10/03)
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- Nickel-catalyzed cross-coupling reaction of alkyl halides with organozinc and grignard reagents with 1,3,8,10-tetraenes as additives
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Essential additives: The addition of bis(1,3-butadienyl) compounds (tetraenes) was essential in the efficient Nicatalyzed cross-coupling of organozinc reagents with alkyl bromides and a tosylate (see scheme, X = C(CO2Me)2 or NCH2Ph). The efficiency of the Ni-catalyzed cross-coupling of an alkyl fluoride with a Grignard reagent was also improved by using these tetraenes.
- Terao, Jun,Todo, Hirohisa,Watanabe, Hideyuki,Ikumi, Aki,Kambe, Nobuaki
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p. 6180 - 6182
(2007/10/03)
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- Suzuki-Miyaura cross-coupling of aryl and alkyl halides using palladium/imidazolium salt protocols
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A simple new protocol for the high yielding Suzuki-Miyaura cross-couplings of aryl chlorides with aryl boronic acids using a palladium/imidazolium salt catalytic system is presented. The first examples of a palladium/imidazolium salt protocol for sp3-sp3 Suzuki-Miyaura couplings of alkyl halides are also disclosed.
- Arentsen, Katherine,Caddick, Stephen,Cloke, F. Geoffrey N.,Herring, Adam P.,Hitchcock, Peter B.
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p. 3511 - 3515
(2007/10/03)
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- Addition of metal cyanides to tosylhydrazones of aldehydes in aprotic solvents: A new method for one-carbon homologation of aldehydes and for the synthesis of α-(N2-tosylhydrazino)nitriles
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One-carbon homologation of aldehydes to nitriles via reaction of the respective tosylhydrazones with trimethylsilyl cyanide, tributyltin cyanide and diethylaluminum cyanide with or without Lewis acid-type catalysts was examined. Representative tosylhydrazones on treatment with trimethylsilyl cyanide in the presence of trimethylsilyl triflate or scandium triflate afforded α-(N2-tosylhydraziono)nitriles in excellent yields. The same adducts were also obtained using tributyltin cyanide/scandium triflate system or diethylaluminum cyanide at room temperature. Treatment of tosylhydrazones with trimethylsilyl cyanide/scandium triflate or with diethylaluminum cyanide in appropriate solvent at higher temperatures afforded the respective one-carbon extended nitriles in good yields. Some examples of the application of these reactions to polyfunctional compounds are given.
- Marczak, Stanis?aw,Wicha, Jerzy
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p. 1049 - 1054
(2007/10/03)
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- Azide and Cyanide Displacements via Hypervalent Silicate Intermediates
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Hypervalent azido- and cyanosilicate derivatives, prepared in situ by the reaction of trimethylsilyl azide or trimethylsilyl cyanide, respectively, with tetrabutylammonium fluoride, are effective sources of nucleophilic azide or cyanide. Primary and secondary alkyl halides and sulfonates undergo rapid and efficient azide or cyanide displacement in the absence of phase transfer catalysts with the silicate derivatives. Application of these reagents to the stereoselective synthesis of glycosyl azide derivatives is reported.
- Soli, Eric D.,Manoso, Amy S.,Patterson, Michael C.,DeShong, Philip,Favor, David A.,Hirschmann, Ralph,Smith III, Amos B.
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p. 3171 - 3177
(2007/10/03)
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- Alkyl isocyanides as precursors for the formation of carbon-carbon bonds
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Tris(trimethylsilyl)silane is an effective mediator for the formation of carbon-carbon bonds via radicals using alkyl isocyanides as precursors.
- Chatgilialoglu,Giese,Kopping
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p. 6013 - 6016
(2007/10/02)
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- GENERATION AND SYNTHETIC USE OF ALKYL RADICALS WITH 2 AS MEDIATOR
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Irradiation of dimeric iron complex 1 in the presence of alkyl halides yields alkyl radicals that are useful in organic synthesis.
- Thoma, Gebhard,Giese, Bernd
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p. 2907 - 2910
(2007/10/02)
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- A REGIOSPECIFIC METHOD FOR THE HYDROCYANATION OF OLEFINS
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A convenient method for the anti-Markovnikov hydrocyanation of olefins utilizing organozirconium chemistry has been developed.This method has been shown to tolerate a wide range of functionality in the substrate olefin.
- Buchwald, Stephen L.,LaMaire, Susan J.
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p. 295 - 298
(2007/10/02)
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