- Hydroborative reduction of amides to amines mediated by La(CH2C6H4NMe2-: O)3
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The deoxygenative reduction of amides to amines is a great challenge for resonance-stabilized carboxamide moieties, although this synthetic strategy is an attractive approach to access the corresponding amines. La(CH2C6H4NMe2-o)3, a simple and easily accessible lanthanide complex, was found to be highly efficient not only for secondary and tertiary amide reduction, but also for the most challenging primary reduction with pinacolborane. This protocol exhibited good tolerance for many functional groups and heteroatoms, and could be applied to gram-scale synthesis. The active species in this catalytic cycle was likely a lanthanide hydride.
- Gong, Mingliang,Guo, Chenjun,Luo, Yunjie,Xie, Hongzhen,Zhang, Fangcao
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p. 779 - 791
(2022/01/22)
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- Electrochemical Synthesis of Allylic Amines from Terminal Alkenes and Secondary Amines
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Allylic amines are valuable synthetic targets en route to diverse biologically active amine products. Current allylic C-H amination strategies remain limited with respect to the viable N-substituents. Herein, we disclose a new electrochemical process to p
- Targos, Karina,Wang, Diana J.,Wickens, Zachary K.
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supporting information
p. 21503 - 21510
(2022/01/03)
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- Deoxygenation of primary amides to amines with pinacolborane catalyzed by Ca[N(SiMe3)2]2(THF)2
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Deoxygenative reduction of amides is a challenging but favorable synthetic method of accessing amines. In the presence of a catalytic amount of Ca[N(SiMe3)2]2(THF)2, pinacolborane (HBpin) could efficiently reduce a broad scope of amides, primary amides in particular, into corresponding amines. Functional groups and heteroatoms showed good tolerance in this process of transformation, and a plausible reaction mechanism was proposed.
- Gong, Mingliang,Guo, Chenjun,Jiang, Linhong,Luo, Yunjie,Yu, Chong
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supporting information
p. 1201 - 1206
(2021/05/29)
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- Reduction of Amides to Amines with Pinacolborane Catalyzed by Heterogeneous Lanthanum Catalyst La(CH2C6H4NMe2- o)3@SBA-15
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Hydroboration of amides is a useful synthetic strategy to access the corresponding amines. In this contribution, it was found that the supported lanthanum benzyl material La(CH2C6H4NMe2-o)3@SBA-15 was highly active for the hydroboration of primary, secondary, and tertiary amides to amines with pinacolborane. These reactions selectively produced target amines and showed good tolerance for functional groups such as -NO2, -halogen, and -CN, as well as heteroatoms such as S and O. This reduction procedure exhibited the recyclable and reusable property of heterogeneous catalysts and was applicable to gram-scale synthesis. The reaction mechanisms were proposed based on some control experiments and the previous literature. This is the first example of hydroborative reduction of amides to amines mediated by heterogeneous catalysts.
- Guo, Chenjun,Zhang, Fangcao,Yu, Chong,Luo, Yunjie
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supporting information
p. 13122 - 13135
(2021/08/31)
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- Homoleptic Bis(trimethylsilyl)amides of Yttrium Complexes Catalyzed Hydroboration Reduction of Amides to Amines
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Homoleptic lanthanide complex Y[N(TMS)2]3 is an efficient homogeneous catalyst for the hydroboration reduction of secondary amides and tertiary amides to corresponding amines. A series of amides containing different functional groups such as cyano, nitro, and vinyl groups were found to be well-tolerated. This transformation has also been nicely applied to the synthesis of indoles and piribedil. Detailed isotopic labeling experiments, control experiments, and kinetic studies provided cumulative evidence to elucidate the reaction mechanism.
- Ye, Pengqing,Shao, Yinlin,Ye, Xuanzeng,Zhang, Fangjun,Li, Renhao,Sun, Jiani,Xu, Beihang,Chen, Jiuxi
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p. 1306 - 1310
(2020/02/22)
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- Catalyst-Free [2,3]-Sigmatropic Rearrangement Reactions of Photochemically Generated Ammonium Ylides
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The rearrangement reaction of ammonium ylides furnishes valuable α,α-disubstituted amino esters. In this work, we describe the visible-light photolysis reaction of aryldiazoacetates in the presence of tertiary amines that react via a free ammonium ylide i
- He, Feifei,Koenigs, Rene M.,Li, Fang
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p. 4348 - 4358
(2019/11/21)
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- Dehydrative Allylation of Amine with Allyl Alcohol by Titanium Oxide Supported Molybdenum Oxide Catalyst
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The dehydrative allylation from allyl alcohol with amines to generate various allyl amines by MoO 3 /TiO 2 solid catalyst is described. The catalyst can be reused at least three times without a decrease of activity.
- Kon, Yoshihiro,Nakashima, Takuya,Fujitani, Tadahiro,Murayama, Toru,Ueda, Wataru
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supporting information
p. 287 - 292
(2019/02/12)
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- B(C6F5)3-Catalyzed Deoxygenative Reduction of Amides to Amines with Ammonia Borane
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The first B(C6F5)3-catalyzed deoxygenative reduction of amides into the corresponding amines with readily accessible and stable ammonia borane (AB) as a reducing agent under mild reaction conditions is reported. This metal-free protocol provides facile access to a wide range of structurally diverse amine products in good to excellent yields, and various functional groups including those that are reduction-sensitive were well tolerated. This new method is also applicable to chiral amide substrates without erosion of the enantiomeric purity. The role of BF3 ? OEt2 co-catalyst in this reaction is to activate the amide carbonyl group via the in situ formation of an amide-boron adduct. (Figure presented.).
- Pan, Yixiao,Luo, Zhenli,Han, Jiahong,Xu, Xin,Chen, Changjun,Zhao, Haoqiang,Xu, Lijin,Fan, Qinghua,Xiao, Jianliang
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supporting information
p. 2301 - 2308
(2019/01/30)
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- METHOD OF PRODUCING TERTIARY AMINE OR TERTIARY AMINE DERIVATIVE
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PROBLEM TO BE SOLVED: To provide a method of producing tertiary amine or tertiary amine derivative with high selectivity. SOLUTION: In the method of producing tertiary amine or tertiary amine derivative, a reaction system including: an organic chemical raw material containing at least one kind of group selected from -NH2, -NH2 HCl, >NH and >NH HCl, a nitrogen atom contained in the group bounding to a carbon atom; aliphatic alcohol having 1 to 20 carbon atoms; and a catalyst where a carrier containing titanium oxide carries a silver component (metal silver or silver compound), is irradiated with light, and the group in the organic compound raw material is converted to -NR02 or >NR0, ( R0 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms derived from the aliphatic alcohol). The percentage content of the silver in the catalyst is 0.5 to 10 mass% with respect to the titanium oxide. COPYRIGHT: (C)2015,JPOandINPIT
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Paragraph 0059; 0060
(2018/10/31)
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- Leaving group potential of a substituted cyclopentadienyl anion toward oxidative addition
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The facility with which a substituted cyclopentadienyl anion may function as a leaving group for palladium-catalyzed allylation reactions Is demonstrated. Reaction of several allylcyclopentadienyl substrates Is shown. Nucleophilic displacement of carbon w
- Fisher, Ethan L.,Lambert, Tristan H.
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supporting information; experimental part
p. 4108 - 4110
(2009/12/06)
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- Why platinum catalysts involving ligands with large bite angle are so efficient in the allylation of amines: Design of a highly active catalyst and comprehensive experimental and DFT study
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The platinum-catalyzed allylation of amines with allyl alcohols was studied experimentally and theoretically. The complexes [Pt(η3-allyl)- (dppe)]OTf (2) and [Pt(η3-allyl)(DPP-Xantphos)]PF6 (5) were synthesized and structurally characterized, and their reactivity toward amines was explored. The bicyclic aminopropyl complex [Pt(CH2CH 2CH2NHBn-κ-C,N)-(dppe)]OTf (3) was obtained from the reaction of complex 2 with an excess of benzylamine, and this complex was shown to be a deactivated form of catalyst 2. On the other hand, reaction of complex 5 with benzylamine and allyl alcohol led to formation of the 16-VE platinum(0) complex [P(η2-C3H3OH)-(DPP-Xantphos)] (7), which was structurally characterized and appears to be a catalytic intermediate. A DFT study showed that the mechanism of the platinum-catalyzed allylation of amines with allyl alcohols differs from the palladium-catalyzed process, since it involves an associative ligand-exchange step involving formation of a tetracoordinate 18-VE complex. This DFT study also revealed that ligands with large bite angles disfavor the formation of platinum hydride complexes and therefore the formation of a bicyclic aminopropyl complex, which is a thermodynamic sink. Finally, a combination of 5 and a proton source was shown to efficiently catalyze the allylation of a broad variety of amines with allyl alcohols under mild conditions.
- Mora, Guilhem,Piechaczyk, Olivier,Houdard, Romaric,Mezailles, Nicolas,Le Goff, Xavier-Frederic,Le Floch, Pascal
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experimental part
p. 10047 - 10057
(2009/11/30)
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- New enantioselective method for hydration of alkenes using cyclodextrins as phase transfer catalyst
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A new enantioselective/inverse phase transfer catalysis (IPTC) reaction for the Markovnikov hydration of double bounds by an oxymercuration-demercuration reaction with cyclodextrins as catalysts was disclosed. Moderate ee (up to 32%) and yields (14-60%) w
- Abreu, Artur R.,Costa, Iva,Rosa, Carla,Ferreira, Luísa M.,Louren?o, Ana,Santos, Pedro P.
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p. 11986 - 11990
(2007/10/03)
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- Ruthenium-Catalyzed Chemoselective N-Allyl Cleavage: Novel Grubbs Carbene Mediated Deprotection of Allylic Amines
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A novel application of the Grubbs carbene complex has been discovered. The first examples of the catalytic deprotection of allylic amines with reagents other than palladium catalysts have been achieved through Grubbs carbene mediated reaction. Significantly, the catalytic system directs the reaction toward the selective deprotection of allylic amines (secondary as well as tertiary) in the presence of allylic ethers. A variety of substrates, including enantiomerically pure multifunctional piperidines, are also usable. The new method is more convenient, chemoselective, and operationally simple than the palladium-catalyzed method. The current mechanistic hypothesis invokes a nitrogen-assisted ruthenium-catalyzed isomerization, followed by hydrolysis of the enamine intermediate. We believe that the reactive species involved in the reaction may be an Ru-H species rather than the Grubbs carbene itself. Thus, the isomerization may occur according to the hydride mechanism. The synthetic utility of this ruthenium-catalyzed allyl cleavage is illustrated by the preparation of indolizidine-type alkaloids.
- Alcaide, Benito,Almendros, Pedro,Alonso, Jose M.
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p. 5793 - 5799
(2007/10/03)
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- Tandem formation and [2,3] rearrangement of methylene ammonium ylides derived from amines and the Simmons-Smith reagent
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(Matrix presented) Zinc-complexed methylene ammonium ylides are formed from tertiary amines and the Simmons-Smith reagent. These stable entities can be activated with n-BuLi to allow reactions typical of ammonium ylides such as [2,3] rearrangements. In th
- Aggarwal, Varinder K.,Fang, Guang Yu,Charmant, Jonathan P. H.,Meek, Graham
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p. 1757 - 1760
(2007/10/03)
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- Phenyl chloro(thionoformate): A new dealkylating agent of tertiary amines
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Phenyl chloro(thionoformate) reacts rapidly with unhindered tertiary aliphatic amines at 20° to give a thiocarbamate and an alkyl chloride. Dialkylcyclohexylamines react surprisingly rapidly to form predominantly cyclohexene. The thiocarbamates are converted into the secondary amine salt by treatment with dimethyl sulfate, followed by hydrolysis with water. Rates of reaction and alkyl group cleavage selectivity in amines were found to be superior or comparable to those previously reported with chloroformates.
- Milan, David S.,Prager, Rolf H.
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p. 841 - 849
(2007/10/03)
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- Nu-alloc temporary protection in solid-phase peptide synthesis. The use of amine-borane complexes as allyl group scavengers
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The use of a combination of amine-borane complexes and soluble palladium catalyst allows the fast deprotection of allyl carbamates under near-to-neutral conditions and without any side-formation of allylamine. Preliminary experiments: indicate that palladium catalyst-amine-borane systems seem ideally suited for removal of Nu-Alloc terminal groups during solid phase peptide synthesis according to the Nu-Alloc temporary protection strategy. The Royal Society of Chemistry 1999.
- Gomez-Martinez, Paloma,Dessolin, Michele,Guibe, Francois,Albericio, Fernando
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p. 2871 - 2874
(2007/10/03)
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- Amination of(η3-allyl)dicarbonylnitrosyliron complexes: A route to γ- amino-α,β-unsaturated carboxylic acid derivatives
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Amines reacted regioselectively with (ν3-allyl)dicarbonylnitrosyliron complexes having ester group on the allyl ligand to give γ-amino-α,β- unsaturated esters in high yields. A remarkable effect of the substituents attached to the allyl ligand was observed on the reaction rate and regioselectivity of the amination. The methoxycarbonyl group significantly accelerates the reaction rate and enhances the regioselectivity of the reaction. The phenyl group retards the reaction, but enhances the regioselectivity, while alkyl groups retard the reaction and diminish the regioselectivity.
- Nakanishi, Saburo,Okamoto, Kenji,Yamaguchi, Hiroshi,Takata, Toshikazu
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p. 1735 - 1741
(2007/10/03)
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- A simple procedure for af-propenylation and af-propynylation of secondary amines
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A number of tertiary N-allyl- and N-propargyl-substituted amines have been prepared by alkylation of secondary amines under solid-liquid phase-transfer catalysis conditions.
- Crock, Piero Dalla,Ferraccioli, Raffaella,Rosa, Concetta L.A.
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p. 107 - 109
(2007/10/03)
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- ?-Allyl palladium methodology for selective deprotection of allylamines. Practical synthesis of secondary amines
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The palladium-promoted deallylation of allylamines derived from primary and secondary amines is achieved with high to quantitative yield in the presence of 2-mercaptobenzoic acid as an allyl scavenger.This method was used for the sequential cleavage of diallylamines.A synthetic application of this procedure is presented in the preparation of secondary amines from diallylamines. - Keywords: allylamine; deallylation; sequential deprotection; ?-allyl palladium complexes; 2-mercaptobenzoic acid; substitution of amines
- Lemarie-Audoire, Sandrine,Savignac, Monique,Dupuis, Christophe,Genet, Jean Pierre
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p. 1157 - 1166
(2007/10/03)
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- Palladium-catalyzed reactions in aqueous media. An efficient removal of allyloxycarbonyl protecting group from oxygen and nitrogen
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The Allyloxycarbonyl (Alloc) moiety can be removed smoothly and selectively in good yield (70-99%) from allylic esters, carbamates and carbonates by aqueous Pd (0) catalyzed allyl transfer to diethylamine as the accepting nucleophile. The method has been successfully used for deprotection of a wide range of secondary amines.
- Genet, Jean Pierre,Blart, Errol,Savignac, Monique,Lemeune, Stephane,Paris, Jean-Marc
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p. 4189 - 4192
(2007/10/02)
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- Aza-Wittig Rearrangements and Cyclizations by Transmetallation of N-Benzylaminomethylstannanes
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Transmetallation of N-allyl-N-benzylaminomethylstannanes with butyllithium or methyllithium allows carbon-carbon bond formation by a -rearrangement.Substantial amounts of the protodestannylated product are also produced.Transmetallation of the corresponding α-methyl substituted allylic amine or homoallylic amine gives an overall rearrangement by cyclization onto the olefin followed by recapture of the new carbanion by tetramethyltin.
- Coldham, Iain
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p. 1275 - 1276
(2007/10/02)
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- Practical palladium-mediated deprotective method of allyloxycarbonyl in aqueous media
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The Allyloxycarbonyl (Alloc) moiety can be removed smoothly and selectively in good yield (73-100%) from allylic esters, carbamates and carbonates by aqueous Pd (O) catalysed allyl transfer to diethylamine in aqueous media employing a water soluble phosphine. The allyl scavenger as well as by product allyl diethylamine are volatile and easily removed in vacuo. In a two phase system an increased selectivity is seen. The method has been successfully used for deprotection of a wide range of secondary amines or base sensitive derivatives and the catalyst is efficiently recycled.
- Genet, Jean Pierre,Blart, Errol,Savignac, Monique,Lemeune, Stephane,Lemaire-Audoire, Sandrine,Paris, Jean-Marc,Bernard, Jean-Marie
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p. 497 - 503
(2007/10/02)
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- Latent inhibitors of aldehyde dehydrogenase as alcohol deterrent agents
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A series of compounds structurally related to pargyline (N-methyl-N-propargylbenzylamide) were synthesized with the propargyl group replaced by a cyclopropyl, allyl, or 2,2,2-trichloroethyl group and, additionally in several cases, with the methyl group r
- Nagasawa,Elberling,DeMaster
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p. 1335 - 1339
(2007/10/02)
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