- Iodine-mediated 1,2-aryl migration of primary benzhydryl amines
-
An iodine-mediated 1,2-aryl migration reaction of primary benzhydryl amines under transition metal-free conditions has been achieved. The crude imines generated by this rearrangement reaction can be directly transformed into various aromatic secondary ami
- Chang, Junbiao,Du, Yangxu,Hao, Wei,Hou, Jiao,Lu, Qing,Yu, Wenquan
-
supporting information
p. 16223 - 16226
(2021/09/22)
-
- Chan-Lam Amination of Secondary and Tertiary Benzylic Boronic Esters
-
We report a Chan-Lam coupling reaction of benzylic and allylic boronic esters with primary and secondary anilines to form valuable alkyl amine products. Both secondary and tertiary boronic esters can be used as coupling partners, with mono-alkylation of the aniline occurring selectively. This is a rare example of a transition-metal-mediated transformation of a tertiary alkylboron reagent. Initial investigation into the reaction mechanism suggests that transmetalation from B to Cu occurs through a single-electron, rather than a two-electron process.
- Dennis, Francesca M.,Grayson, James D.,Partridge, Benjamin M.,Robertson, Craig C.
-
p. 9883 - 9897
(2021/07/20)
-
- In Water Markovnikov Hydration and One-Pot Reductive Hydroamination of Terminal Alkynes under Ruthenium Nanoparticle Catalysis
-
In the presence of Shvo's catalyst [2,3,4,5-tetraphenyl-1,3-cyclopentadien-1-ol, ruthenium(II) complex], a small quantity of aniline and TGPS-750-M surfactant, terminal alkynes were hydrated under microwave (MW) dielectric heating in water as solvent with high conversion and good yield. The reaction gives the Markovnikov product exclusively, unlike that commonly observed with ruthenium complexes. Under the influence of MWs, Ru nanoparticles embedded in the nanomicelle environment were formed, acting as the effective hydration catalyst. Introducing sodium formate in the aqueous phase and using a stoichiometric amount of amines, the Ru nanoparticle nanomicelle catalyst gave the first example of one-pot single-step hydroamination of alkynes with the formation of the corresponding secondary amines. The reaction is characterized by low environmental impact as TGPS-750-M is required in low amount, and organic solvents employed only for product separation or catalyst recycling.
- Risi, Caterina,Cini, Elena,Petricci, Elena,Saponaro, Simone,Taddei, Maurizio
-
supporting information
p. 1000 - 1003
(2020/01/22)
-
- Diethylsilane as a Powerful Reagent in Au Nanoparticle-Catalyzed Reductive Transformations
-
Diethylsilane (Et2SiH2), a simple and readily available dihydrosilane, that exhibits superior reactivity, as compared to monohydrosilanes, in a series of reductive transformations catalyzed by recyclable and reusable Au nanoparticles (1 mol-%) supported on TiO2. It reduces aldehydes or ketones almost instantaneously at ambient conditions. It can be used in a one pot rapid reductive amination procedure, in which premixing of aldehyde and amine is required prior to the addition of the reducing agent and the catalyst, even in a protic solvent. An unprecedented method for the synthesis of N-arylisoindolines is also shown in the reductive amination between o-phthalaldehyde and anilines. In this transformation, it is proposed that the intermediate N,2-diphenylisoindolin-1-imines are reduced stepwise to the isoindolines. Finally, Et2SiH2 readily reduces amides into amines in excellent yields and shorter reaction times relative to previously known analogous nano Au(0)-catalyzed protocols.
- Louka, Anastasia,Kidonakis, Marios,Saridakis, Iakovos,Zantioti-Chatzouda, Elisavet-Maria,Stratakis, Manolis
-
p. 3508 - 3514
(2020/06/02)
-
- Iron-catalyzed reductive coupling of nitroarenes with olefins: Intermediate of iron-nitroso complex
-
Using a single half-sandwich iron(II) compound, CpFe(1,2-Ph2PC6H4S)(NCMe) (Cp- = C5Me5-, 1) as a catalyst, reductive coupling of nitroarenes with olefins has been achieved by a well-defined iron(II)/(EtO)3SiH system. Through either inter- or intramolecular reductive coupling, various branched amines and indole derivatives have been directly synthesized in one-pot. Mechanistic studies showed that the catalysis is initiated by activation of nitroarenes by the iron(II) catalyst with silane, generating iron-nitrosoarene intermediate for the C-N bond coupling.
- Song, Heng,Yang, Zhuoyi,Tung, Chen-Ho,Wang, Wenguang
-
p. 276 - 281
(2019/12/24)
-
- Development of [3]ferrocenophane-derived N/B frustrated Lewis pairs for the metal-free catalytic hydrogenation of imines
-
A series of novel [3]ferrocenophane-derived N/B frustrated Lewis pairs (FLPs) were synthesized and successfully applied to the catalytic hydrogenation of imines in 71–93% yields. This approach could be easily conducted on gram scale and provided versatile synthetic route for the key intermediate of sertraline hydrochloride without heavy metal residues.
- Pan, Zhentao,Wang, Hui,Ling, Fei,Xiao, Lian,Song, Dingguo,Zhong, Weihui
-
p. 522 - 528
(2019/02/01)
-
- Visible-Light-Induced Copper-Catalyzed Intermolecular Markovnikov Hydroamination of Alkenes
-
A visible-light-induced copper-catalyzed intermolecular hydroamination of alkenes using commercially accessible primary and secondary amines has been established. This effective method exhibits good tolerance of a broad range of functional groups and provides a facile access to an array of valuable amines with Markovnikov regioselectivity. The process can be positively expected to be used in bioactive amines, and it may provide new potential in the discovery of copper-catalyzed hydrofunctionalization reactions.
- Xiong, Yang,Zhang, Guozhu
-
supporting information
p. 7873 - 7877
(2019/10/10)
-
- Cobalt-Catalyzed Hydroarylations and Hydroaminations of Alkenes in Tunable Aryl Alkyl Ionic Liquids
-
Tunable aryl alkyl ionic liquids (TAAILs) are a promising class of imidazolium- or triazolium-based ionic liquids. Contrary to "standard" all-alkyl ionic liquids, these carry an aryl ring together with a linear or branched alkyl chain. Their application i
- Schroeter, Felix,Lerch, Swantje,Kaliner, Maria,Strassner, Thomas
-
supporting information
p. 6215 - 6219
(2018/10/05)
-
- N,N-coordination Rh complex as well as synthesis method and application thereof
-
The invention belongs to the technical field of synthesis of organic metal compounds and particularly relates to an N,N-coordination Rh complex as well as a synthesis method and an application thereof. Firstly, a ligand is synthesized from methyl 1H-pyrrole-2-carboxylate as an initial raw material and further reacts with Rh(COD)2Cl, and a metal complex with Rh as a central atom is obtained. The synthesis method is simple, the complex as a catalyst can be used for catalyzing a series of reductive amination reactions of derivatives of acetophenone and aniline, and the product yield is good and is 90% or above.
- -
-
Paragraph 0091; 0092; 0093
(2018/03/28)
-
- Enhanced Catalytic Activity of Oxygen-Tethered IrIII NHC Complexes in Aqueous Transfer Hydrogenative Reductive Amination Reactions: Experimental Kinetic and Mechanistic Study
-
The synthesis and characterization of seven new IrIII complexes containing o-phenoxide or o-naphthoxide chelated N-heterocyclic carbene ligands is reported herein. The crystal structures of six of the complexes have been determined. These complexes efficiently catalyze the transfer hydrogenative reductive amination (RA) of carbonyls and amines in water. Amongst the complexes tested, the introduction of o-naphthoxide on a nitrogen atom of imidazole based NHC ligand greatly increased the catalytic activity. The catalytic system has a broad substrate scope, which allows the synthesis of a variety of amines in excellent yields and with high turnover numbers up to 490 (for ketones) and 14800 (for aldehydes). The mechanism of aqueous RA reaction with an o-aryloxide chelated NHC-IrIII catalyst has been investigated by NMR spectroscopy and kinetic measurements. These studies suggest that the transfer hydrogenation (TH) is turnover-limited by the hydride formation step. As a result of the 1H NMR studies, the higher catalytic activity of o-naphthoxide chelated catalyst (3 g) over o-phenoxide chelated one (3 b) can be attributed partly due to the faster formation of an iridium hydride, the key intermediate in the RA reactions.
- ?zbozkurt, ?brahim Kayahan,Gülcemal, Derya,Günnaz, Salih,G?k?e, Ayta? Gürhan,?etinkaya, Bekir,Gülcemal, Süleyman
-
p. 3593 - 3604
(2018/08/03)
-
- Hofmann N-alkylation of aniline derivatives with alcohols using ferric perchlorate immobilized on SiO2 as a catalyst through Box–Behnken experimental design
-
An efficient method for the N-alkylation of poorly nucleophilic amines using ferric perchlorate immobilized on SiO2 as a catalyst is described. Fe(ClO4)3 was prepared from mixing iron(III) hydroxide and perchloric acid and adsorbed on silica gel. The catalyst was characterized using various techniques. The supported ferric perchlorate (Fe(ClO4)3/SiO2) revealed high efficiency and selectivity for N-alkylation of aromatic amines with alcohols to provide alkylated amines. Various secondary amines were synthesized from primary amines and alcohols in good to excellent yields, with water as the only by-product. The optimization of the reaction conditions was investigated using the response surface method, and involving the Box–Behnken design matrix. The conditions for optimal reaction yield and time were: amount of catalyst?=?0.34?mmol, temperature?=?60°C and molar ratio of amine to alcohol?=?1.2. The catalyst was recovered and reused for five cycles without a considerable decrease in catalytic activity. The stability of the recycled catalyst was investigated. The proposed method has numerous advantages including procedure simplicity, short reaction times, low cost, good to excellent yields, reusability of the catalyst and mild and environmentally benign conditions.
- Ghanimati, Mahdi,Abdoli Senejani, Masumeh,Isfahani, Tahereh Momeni,Bodaghifard, Mohammad Ali
-
-
- Commercial Supported Gold Nanoparticles Catalyzed Alkyne Hydroamination and Indole Synthesis
-
Commercial gold nanoparticles supported on titanium dioxide (TiO2) were found to be a highly efficient catalyst for alkyne hydroamination. Terminal alkynes could easily undergo intermolecular hydroamination with low catalyst loadings (0.2 mol% Au) under solvent-free conditions. Indoles were efficiently synthesized using microwave heating through intramolecular hydroamination. (Figure presented.).
- Liang, Shengzong,Hammond, Luisa,Xu, Bo,Hammond, Gerald B.
-
p. 3313 - 3318
(2016/10/21)
-
- Nickel(II) complex covalently anchored on core shell structured SiO2@Fe3O4 nanoparticles: A robust and magnetically retrievable catalyst for direct one-pot reductive amination of ketones
-
A robust and efficient core shell structured magnetically retrievable nickel nanocatalytic system was fabricated via the covalent immobilization of 2-acetyl furan on the surface of an amine functionalized silica coated magnetic nanosupport followed by its metallation with nickel acetate. The newly synthesized magnetic silica based organic-inorganic hybrid nanocatalyst (Ni-ACF@Am-SiO2@Fe3O4) was systematically affirmed using several physico-chemical characterization tools such as FT-IR, XRD, VSM, SEM, TEM, EDS, ED-XRF and AAS. Thereafter, the catalytic performance of this Ni-ACF@Am-SiO2@Fe3O4 nanocatalyst was investigated in the one-pot reductive amination of ketones using NaBH4 as the reductant under neat conditions. The developed core shell magnetic silica based nickel nanocatalyst successfully afforded a structurally diverse range of secondary amines with high turnover frequency (TOF) and excellent conversion percentage. Additionally, it was found that this catalyst could not only be retrieved from the reaction vessel within a fraction of seconds using an external magnet but also be recycled for multiple runs without any discernible loss in its activity that rendered this protocol superior to all the previously established methodologies for the one-pot synthesis of substituted amines. Besides, some of the other fascinating features of this methodology that made it a potential candidate for addressing various economic and environmental concerns were ambient reaction conditions, broad substrate scope, simple workup procedure, shorter reaction time and cost effectiveness.
- Sharma, Rakesh Kumar,Dutta, Sriparna,Sharma, Shivani
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p. 2089 - 2101
(2016/03/19)
-
- Highly Stable Mesoporous Zirconium Porphyrinic Frameworks with Distinct Flexibility
-
The construction of highly stable metal-porphyrinic frameworks (MPFs) is appealing as these materials offer great opportunities for applications in artificial light-harvesting systems, gas storage, heterogeneous catalysis, etc. Herein, we report the synthesis of a novel mesoporous metal-porphyrinic framework (denoted as NUPF-1) and its catalytic properties. NUPF-1 is constructed from a new porphyrin linker and a Zr6O8 structural building unit, possessing an unprecedented doubly interpenetrating scu net. The structure exhibits not only remarkable chemical and thermal stabilities, but also a distinct structural flexibility, which is seldom seen in metal-organic framework (MOF) materials. By the merit of high chemical stability, NUPF-1 could be easily post-metallized with [Ru3(CO)12], and the resulting {NUPF-1-RuCO} is catalytically active as a heterogeneous catalyst for intermolecular C(sp3)-H amination. Excellent yields and good recyclability for amination of small substrates with various organic azides have been achieved.
- Xu, Lei,Luo, Yan-Ping,Sun, Lin,Xu, Yan,Cai, Zhong-Sheng,Fang, Min,Yuan, Rong-Xin,Du, Hong-Bin
-
supporting information
p. 6268 - 6276
(2016/05/02)
-
- Mechanistic studies on the alkylation of amines with alcohols catalyzed by a bifunctional iridium complex
-
The mechanism of the N-alkylation of amines with alcohols catalyzed by an iridium complex containing an N-heterocyclic carbene (NHC) ligand with a tethered alcohol/alkoxide functionality was investigated by a combination of experimental and computational methods. The catalyst resting state is an iridium-hydride species containing the amine substrate as a ligand, and decoordination of the amine, followed by coordination of the imine intermediate to the iridium center, constitute the rate-determining step (rds) of the catalytic process. The alcohol/alkoxide that is tethered to the NHC participates in every step of the catalytic cycle by accepting or releasing protons and forming hydrogen bonds with the reacting species. Thus, the iridium complex with the alcohol/alkoxide tethered to the N-heterocyclic carbene ligand acts as a bifunctional catalyst.
- Bartoszewicz, Agnieszka,González Miera, Greco,Marcos, Roc?o,Norrby, Per-Ola,Mart?n-Matute, Belén
-
p. 3704 - 3716
(2015/06/16)
-
- CATALYST COMPOUNDS
-
The present invention relates to an iridium-based catalyst compound for hydrogenating reducible moieties, especially imines and iminiums, the catalyst compounds being defined by the formulas: where ring B is either itself polycyclic, or ring B together with R is polycyclic. The catalysts of the invention are particularly effective in reductive amination procedures 10 which involve the in situ generation of the imine or iminium under reductive hydrogenative conditions.
- -
-
Paragraph 0314; 0325
(2015/03/28)
-
- Br?nsted acid catalyzed monoalkylation of anilines with trichloroacetimidates
-
Trichloroacetimidates are useful alkylating agents for aromatic amines, requiring only a catalytic amount of a Br?nsted acid to facilitate the reaction. Monoalkylation predominates under these conditions. Electron-poor anilines provide superior yields, with electron-rich anilines sometimes showing competitive Friedel-Crafts alkylation. A single flask protocol with formation of the imidate in situ is demonstrated, providing a convenient method for the direct substitution of alcohols with anilines. Reaction with a chiral imidate favors a mechanism that proceeds through a carbocation intermediate.
- Wallach, Daniel R.,Stege, Patrick C.,Shah, Jigisha P.,Chisholm, John D.
-
p. 1993 - 2000
(2015/02/19)
-
- Bis(2-cycloazylindolyl)titanium Complexes: Synthesis, Characterization, and the Catalytic Behaviors towards Hydroamination and Ring-opening Polymerization of ε-Caprolactone
-
The ligands 2-pyrazol-1-yl-1H-indole (HL1) and 2-1,2,4-triazol-1-yl-1H-indole (HL2) individually reacted with Ti(NMe2)4 in tetrahydrofuran to form the corresponding complexes Ti(L1)2(NMe2)2 (1) and Ti
- Zhao, Jing-Jing,Pei, Hao,Chen, Yan-Mei,Lu, Ning,Liu, Jin-Na,Hu, Jin-Fa,Liu, Wei,Li, Wu,Li, Yahong
-
p. 1322 - 1328
(2015/06/30)
-
- Indium-catalyzed hydroamination/hydrosilylation of terminal alkynes and aromatic amines through a one-pot, two-step protocol
-
We demonstrated that indium tribromide effectively functioned as a single catalyst for two successive steps in a one-pot procedure. First, the hydroamination of alkynes with anilines took place to give the Markovnikov product. Then, hydrosilylation of the imine intermediates by treatment with a hydrosilane substrate afforded the corresponding secondary amines.
- Sakai, Norio,Takahashi, Nobuaki,Ogiwara, Yohei
-
supporting information
p. 5078 - 5082
(2014/08/18)
-
- Simple and efficient AuI-based catalyst for hydroamination of alkynes
-
Hydroamination of terminal alkynes with anilines in the presence of (C6F5)3PAuNTf2 catalyst affords 2-aryliminoalkanes whose reduction in situ with sodium borohydride gives the corresponding secondary amines in
- Anokhin, Maksim V.,Murashkina, Arina V.,Averin, Alexei D.,Beletskaya, Irina P.
-
p. 332 - 333
(2015/02/19)
-
- Comparative hydroamination of aniline and substituted anilines with styrene on different zeolites, triflate based catalysts and their physical mixtures
-
Catalytic performances of different zeolites (Beta and mordenites), scandium triflate based catalysts, mesoporous UVM-7 encapsulated scandium triflate and physical mixtures prepared under ultrasound irradiation were evaluated in the hydroamination of aniline and substituted anilines with styrene. The performances of these catalysts were controlled by the type of acidity and strength. Thus, the conversion was mainly controlled by the strength of the acid sites and their accessibility, while the selectivity appeared to be controlled by the Lewis/Br?nsted type of acidity. Lewis acid catalysts directed the reactions mainly to the formation of the Markovnikov adducts while Br?nsted acid catalysts to anti-Markovnikov. Zeolites and scandium triflate led to results very close to those reported in the literature. Among different physical mixtures those of scandium triflate with the mesoporous scandium triflate embedded in a UVM-7 structure provided better conversions with a good selectivity in the Markovnikov adduct. These results were attributed to a better dispersion of scandium triflate during the preparation of physical mixtures.
- Ciobanu,Tirsoaga,Amoros,Beltran,Coman,Parvulescu
-
p. 230 - 235
(2014/05/06)
-
- Simple, efficient and reusable Pd-NHC catalysts for hydroamination
-
A series of chelating NHC-palladium complexes with different alkane-bridges of the type Pd[NHC-(CH2)n-NHC]X2 (X = Br or Cl, n = 2-4) were synthesized, where NHC is a triazolyl-N-heterocyclic carbene donor ligand. The bromi
- Chen, Qian,Lv, Lanlan,Yu, Meng,Shi, Yanhui,Li, Yuling,Pang, Guangsheng,Cao, Changsheng
-
p. 18359 - 18366
(2013/10/21)
-
- CATALYST COMPOUNDS
-
The present invention relates to an iridium-based catalyst compound for hydrogenating reducible moieties, especially imines and iminiums, the catalyst compounds being defined by the formulas: where ring B is either itself polycyclic, or ring B together with R is polycyclic. The catalysts of the invention are particularly effective in reductive amination procedures 10 which involve the in situ generation of the imine or iminium under reductive hydrogenative conditions.
- -
-
Paragraph 00163; 00174
(2013/11/05)
-
- Fast reductive amination by transfer hydrogenation "on water"
-
Reductive amination of various ketones and aldehydes by transfer hydrogenation under aqueous conditions has been developed, by using cyclometallated iridium complexes as catalysts and formate as hydrogen source. The pH value of the solution is shown to be critical for a high catalytic chemoselectivity and activity, with the best pH value being 4.8. In comparison with that in organic solvents, the reductive amination in an aqueous phase is faster, and the molar ratio of the substrate to the catalyst (S/C) can be set as high as 1×105, the highest S/C value ever reported in reductive amination reactions. The catalyst is easy to access and the reaction is operationally simple, allowing a wide range of ketones and aldehydes to react with various amines in high yields. The protocol provides a practical and environmental friendly new method for the synthesis of amine compounds. Greener amine synthesis: A versatile reductive amination protocol has been developed. By using an iridium catalyst in water, a broad range of ketones and aldehydes react with amines to afford various new amines in good yields (see scheme), with molar ratios of the substrate to the catalyst (S/C) as high as 1×10 5. The pH of the reaction solution plays a key role, regulating both the catalytic activity and the selectivity. Copyright
- Lei, Qian,Wei, Yawen,Talwar, Dinesh,Wang, Chao,Xue, Dong,Xiao, Jianliang
-
supporting information
p. 4021 - 4029
(2013/04/10)
-
- Rhodium(III)-catalyzed hydroamination of aromatic terminal alkynes with anilines
-
The dinuclear Rh(III) species [Cp*RhCl2]2 catalyzes the hydroamination reaction between an aromatic terminal alkyne (ArCCH) and an aniline (Ar′NH2), in the presence of a salt additive, to afford the ketimine Ar′N=C(Me)(Ar). A reaction pathway has been proposed on the basis of experimental and computational studies.
- Kumaran, Elumalai,Leong, Weng Kee
-
p. 1068 - 1072
(2012/04/04)
-
- Gallium trichloride catalyzed hydroamination of alkynes: Scope, limitation, and mechanistic studies by dft
-
The successful application of gallium trichloride as a catalyst for the intermolecular hydroamination of alkynes with aromatic amines is reported. The reaction is effective with many aniline derivatives and shows exclusive selectivity for the Markovnikov
- Li, Lei,Huang, Genping,Chen, Zhou,Liu, Wei,Wang, Xiufang,Chen, Yanmei,Yang, Lijuan,Li, Wu,Li, Yahong
-
p. 5564 - 5572
(2012/11/07)
-
- Titanium amido- and imido-complexes supported by a tridentate pyrrolyl ligand: Syntheses, characterisation and catalytic activities
-
The complexes [Ti(NMe2)2(pmpmi)] [H2pmpmi = (2-pyrrolylmethene)-(2-pyrrolylmethyl)imine], [Ti(NtBu)(pmpmi)(py) 2], [Ti(NtBu)(pmpmi)(dpy)] and [Ti(NPh)(pmpmi)(py) 2] have been prepared, characterised and shown to be pre-catalysts for the hydroamination of phenylacetylene with aniline and p-chloroaniline. The X-ray structures of [Ti(NMe2)2(pmpmi)], [Ti(N tBu)(pmpmi)(dpy)] and [Ti(NPh)(pmpmi)(py)2] have been determined.
- Chen, Zhou,Li, Lei,Chen, Yanmei,Hu, Bin,Wu, Jian,Wang, Xiufang,Lei, Tao,Li, Yahong
-
experimental part
p. 249 - 253
(2012/09/25)
-
- Catalytic C-H Amination with aromatic amines
-
Aniline joins the club: A β-diketiminato copper(I) catalyst enables C-H amination of anilines employing low catalyst loadings to preclude oxidation to the diazene ArNi-NAr (see scheme). Electron-poor anilines are particularly resistant towards diazene formation and participate in the amination of strong and unactivated C-H bonds. N-alkyl anilines also take part in C-H amination. Copyright
- Gephart III, Raymond T.,Huang, Daria L.,Aguila, Mae Joanne B.,Schmidt, Graham,Shahu, Andi,Warren, Timothy H.
-
supporting information; experimental part
p. 6488 - 6492
(2012/07/30)
-
- Highly selective mono-N-benzylation and amidation of amines with alcohols or carboxylic acids using the Ph2PCl/I2/imidazole reagent system
-
Chlorodiphenylphosphine, imidazole, and molecular iodine in refluxing dichloromethane are used for the efficient preparation of amides under mild reaction conditions. This reagent system also shows excellent selectivity for mono-N-alkylation of amines with alcohols. In this system, the resulting phosphorus byproduct (diphenylphosphinic acid) is easily removed by extraction using an aqueous basic solution in the workup processes, which avoids the tedious and time-consuming chromatographic methods.
- Nowrouzi, Najmeh,Jonaghani, Mohammad Zareh
-
experimental part
p. 498 - 509
(2012/07/30)
-
- Zinc triflate-catalyzed intermolecular hydroamination of vinylarenes and anilines: Scopes and limitations
-
Intermolecular hydroamination of vinylarenes and anilines was studied using zinc triflate as catalyst. NMR experiments supported a Lewis acid activation of the CC double bond. Electronic/steric effect study indicated that Lewis acidity of the catalyst as well as the coordination property of the amine were the governing factors for successful hydroamination of the substrates. More nucleophilic amine would bind more tightly to the central metal, leading to an unproductive coordination. Approach of bulky amine to CC bond would be hindered, and an alternative electrophilic substitution on benzene ring of the amine would become the major reaction. Electrophilic substitution would become predominant when strong electron-donating group is presented on aniline benzene ring.
- Liu, Gong-Qing,Li, Yue-Ming
-
experimental part
p. 7168 - 7170
(2012/01/04)
-
- Highly enantioselective synthesis of chiral secondary amines by gold(I)/ chiral bronsted acid catalyzed tandem intermodular hydroamination and transfer hydrogenation reactions
-
A method for the synthesis of enantiomerically enriched secondary amines with excellent ee values through the tandem intermolecular hydroamination/ transfer hydrogenation of alkynes using a "gold(I) complex-chiral Bronsted acid" protocol is developed. The
- Liu, Xin-Yuan,Che, Chi-Ming
-
supporting information; experimental part
p. 4204 - 4207
(2009/12/31)
-
- A simple catalyst for the efficient benzylation of arenes by using alcohols, ethers, styrenes, aldehydes, or ketones
-
The compound [IrCp* (OTf)2(InBu)] (I nBu = 1,3-di-n-butyl-imidazolylidene) is an effective catalyst in the benzylation of arenes with different benzylating agents, such as alcohols, ethers and styrenes, representing an unprecedented highly versatile catalyst for this type of process. The same compound also catalyses a remarkable tandem process that allows the use of aldehydes and ketones as benzylating agents, through the base-free hydrogenation of C=O bonds with iPrOH and further use of the resulting primary or secondary alcohols as benzylating agents.
- Prades, Amparo,Corberan, Rosa,Poyatos, Macarena,Peris, Eduardo
-
experimental part
p. 4610 - 4613
(2009/12/26)
-
- Development of highly enantioselective new Lewis basic N-formamide organocatalysts for hydrosilylation of imines with an unprecedented substrate profile
-
l-Pipecolinic acid derived N-formamides have been developed as new Lewis basic organocatalysts that promote the asymmetric reduction of N-aryl ketimines using trichlorosilane as the reducing agent. The substituent on N4 of the piperazinyl backbone and the
- Wu, Pengcheng,Wang, Zhouyu,Cheng, Mounuo,Zhou, Li,Sun, Jian
-
experimental part
p. 11304 - 11312
(2009/04/06)
-
- Intermolecular hydroamination of vinyl arenes using tungstophosphoric acid as a simple and efficient catalyst
-
The intermolecular hydroamination of vinyl arene derivatives has been efficiently carried out using a tungstophosphoric acid (TPA) catalyst under solvent free and mild reaction conditions. The present protocol provides an environmentally benign, easy to handle and highly active solid acid catalyst for hydroamination of vinyl arenes. The catalyst yields both hydroamination and hydroarylation products and the selectivity mostly depends on the reaction conditions.
- Seshu Babu,Mohan Reddy,Sai Prasad,Suryanarayana,Lingaiah
-
p. 7642 - 7645
(2008/03/14)
-
- HI-catalyzed hydroamination and hydroarylation of alkenes
-
Aromatic amines react with alkenes in the presence of catalytic amounts of aqueous HI to give mixtures ef the corresponding hydroamination and hydroarylation products. While the hydroamination reaction is the preferred pathway for aliphatic alkenes, the h
- Marcsekova, Klaudia,Doye, Sven
-
p. 145 - 154
(2007/12/27)
-
- Reductive amination of carbonyl compounds using NaBH4 in a Br?nsted acidic ionic liquid
-
Reductive amination of carbonyl compounds using sodium borohydride is conducted in the Br?nsted acidic ionic liquid, 1-methyl imidazolium tetrafluoroborate ([HMIm][BF4]). The ionic liquid plays the dual role of solvent as well as catalyst for efficient conversion of aldehydes and ketones to amines in excellent yields without the formation of side products.
- Reddy, P. Srinivasa,Kanjilal, Sanjit,Sunitha,Prasad, Rachapudi B.N.
-
p. 8807 - 8810
(2008/03/18)
-
- Titanium-catalyzed intermolecular hydroamination of vinylarenes
-
(Chemical Equation Presented) The Lewis acid TiCl4 allows the intermolecular hydroamination of vinylarenes (see scheme). Some of the hydroamination products undergo rearrangements to give ortho-alkylated compounds. The catalyst tolerates a rang
- Kaspar, Ludwig T.,Fingerhut, Benjamin,Ackermann, Lutz
-
p. 5972 - 5974
(2007/10/03)
-
- Direct and indirect reductive amination of aldehydes and ketones with solid acid-activated sodium borohydride under solvent-free conditions
-
A simple and convenient procedure for reductive amination of aldehydes and ketones using sodium borohydride activated by boric acid, p-toluenesulfonic acid monohydrate or benzoic acid as reducing agent under solvent-free conditions is described.
- Byung, Tae Cho,Sang, Kyu Kang
-
p. 5725 - 5734
(2007/10/03)
-
- Air- and moisture-stable cationic (diphosphine)palladium(II) complexes as hydroamination catalysts X-ray crystal structures of two complexes
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A series of cationic (diphosphine)palladium(II) complexes have been prepared and fully characterized, including two crystal structures. These complexes were evaluated as catalysts for the hydroamination of acyclic alkenes. The reactivity of the catalysts is dependent on the nature of the diphosphine ligand and the substituents on the amine and alkene substrates.
- Li, Kelin,Horton, Peter N.,Hursthouse, Michael B.,Hii, King Kuok Mimi
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p. 250 - 257
(2007/10/03)
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- Chemoselective reductive amination of aldehydes and ketones by dibutylchlorotin hydride-HMPA complex
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Reductive amination of various aldehydes and ketones has been performed effectively by pentacoordinate chloro-substituted tin hydride complex, Bu2SnClH-HMPA. The tin reagent worked particularly well for the case using weakly basic aromatic amines as starting substrates. Stoichiometric amounts of a substrate and a reducing agent were adequate for the reaction. The Sn-Cl bond in the complex plays an important role for both steps of imine formation and subsequent reduction. Highly chemoselective reduction of carbonyls could be achieved regardless of other functionalities such as halogen, carbon- carbon double bond and hydroxyl groups in the starting carbonyls and amines.
- Suwa, Toshihiro,Sugiyama, Erika,Shibata, Ikuya,Baba, Akio
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p. 789 - 800
(2007/10/03)
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- Nucleophilic Substitution Reaction of 1-Phenylethyl Chlorides in Methanol
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Nucleophilic substitution reactions of 1-(Y-phenyl)ethyl chlorides with X-anilines have been investigated in methanol at 65.0 deg C.An isokinetic point is obtained at ?Y+ = ca. -0.23 with ρX = 0; the sign of ρX changes at this point from positive for the relatively strong electron donating Y substituents to negative for the more electron withdrawing Y substituents. The magnitude of the cross-interaction constant, ρXY, between the substituents X and Y is unusually large with the relatively small magnitude of ρXo resulting in an observable isokinetic point at .These results are interpreted in terms of a transition state (TS) structure in which nearly complete bond formation between the nucleophile and cation formed in an ion-pair preequilibrium is coupled with a TS imbalance phenomenon.The results of kinetic isotope effect studies involving deuteriated anilines and methanol are also in line with this mechanism.
- Lee, Ikchoon,Lee, Won Heui,Lee, Hai Whang,Bentley, T. W.
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p. 141 - 146
(2007/10/02)
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- Antioxidant for polyester fluids - alpha - methyl - n phenylbenzenemethanamine
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An antioxidant for lubricating oils comprising an amine compound selected from substituted benzylamines or a substituted 1-amino-1,2,3,4-tetrahydro-naphthalene. The preferred anti-oxidants are N-(alpha -methyl -p -octylbenzyl) aniline, N-(alpha-methylbenz
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- Nucleophilic Substitiution Reactions of 1-Phenylethyl Benzenesulfonates with Anilines in Methanol-Acetonitrile
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Nucleophilic substitution reactions of 1-phenylethyl benzenesulfonates with anilines have been investigated in methanol-acetonitrile mixtures at 25 deg C.Magnitudes of the Hammett coefficients ρX, ρY, and ρZ indicate that
- Lee, Ikchoon,Kim, Hyung Yoon,Kang, Han Keun,Lee, Hai Whang
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p. 2678 - 2683
(2007/10/02)
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