- Intramolecular cooperativity in frustrated Lewis pairs
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The doubly Lewis-acid functionalised aniline PhN[(CH2)3B(C6F5)2]2 features two competing boron functions in fast exchange for binding to the central Lewis base. It shows catalytic activity typical for FLPs in H/D-scrambling and catalytic hydrogenation experiments. By contrast, the singly acid-functionalised PhMeN(CH2)3B(C6F5)2 reveals a dramatically smaller catalytic activity in analogous experiments.
- K?rte, Leif A.,Blomeyer, Sebastian,Heidemeyer, Shari,Mix, Andreas,Neumann, Beate,Mitzel, Norbert W.
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Read Online
- Copper-Catalyzed Allylation of Amines with Cyclopropyldiphenylsulfonium Trifluoromethanesulfonate
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Cyclopropyldiphenylsulfonium salt, a famous ylide precursor previously extensively employed in the preparation of cyclic compounds, has been successfully utilized as an efficient allylation reagent in this work. The copper-catalyzed reactions of cyclopropyldiphenylsulfonium trifluoromethanesulfonate with amines in the presence of an appropriate ligand provided the N-allylated products in good yields. Aliphatic/ aromatic amines and primary/secondary amines were all converted under mild reaction conditions. This protocol was also applicable to N-functionalization of drug molecules, supplying the corresponding N-allylated compounds in satisfactory yields. The reaction, which showed good functional group tolerance with a wide range of substrates and excellent chemoselectivity, offers an interesting method for the synthesis of N-allyl amines.
- Ma, Yu,Tian, Ze-Yu,Zhang, Cheng-Pan,Zheng, Shuang-Yang
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- A base-free Chan–Lam reaction catalyzed by an easily assembled Cu(II)-carboxylate metal-organic framework
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A new copper(II) metal-organic framework is constructed as a sustainable copper heterogeneous catalyst. Cu-DPTCA, with high catalytic activity, can effectively promote the Chan–Lam coupling reaction of arylboronic acids and amines without adding any base or additive.
- Ma, Ruixuan,Qin, Jianhua,Shi, Lei,Zhang, Xinhai
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p. 795 - 799
(2021/07/06)
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- Highly efficient Ru(ii)-alkylidene based Hoveyda-Grubbs catalysts for ring-closing metathesis reactions
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Three novel phosphine-free Ru-alkylidenes (7a-7c) have been synthesized and utilized as efficient catalysts for ring closing metathesis (RCM) reaction. Spectroscopic data, i.e. NMR and HRMS, along with single crystal X-ray diffraction analysis, were used
- Al-Awadi, Nouria A.,Al-Enezi, Mariam Y.,Ibrahim, Yehia A.,John, Elizabeth
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p. 37866 - 37876
(2021/12/09)
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- Heterobimetallic Eu(iii)/Pt(ii) single-chain nanoparticles: a path to enlighten catalytic reactions
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We introduce the formation and characterization of heterometallic single-chain nanoparticles entailing both catalytic and luminescent properties. A terpolymer containing two divergent ligand moieties, phosphines and phosphine oxides, is synthesized and intramolecularly folded into nanoparticlesviaa selective metal complexation of Pt(ii) and Eu(iii). The formation of heterometallic Eu(iii)/Pt(ii) nanoparticles is evidenced by size exclusion chromatography, multinuclear NMR (1H,31P{1H},19F,195Pt) as well as diffusion-ordered NMR and IR spectroscopy. Critically, we demonstrate the activity of the SCNPs as a homogeneous and luminescent catalytic system in the amination reaction of allyl alcohol.
- Barner-Kowollik, Christopher,Kn?fel, Nicolai D.,Kulendran, Bragavie,Roesky, Peter W.,Rothfuss, Hannah,Tzvetkova, Pavleta
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p. 10331 - 10336
(2020/10/18)
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- RED FLUORESCENT PROBE FOR USE IN DETECTION OF PEPTIDASE ACTIVITY
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[Problem] A problem addressed by the present invention is to provide a novel fluorescent probe having excellent tissue permeability that is capable of detecting the peptidase activity expressed at a high level in cancer cells and the like as a response of long-wavelength red fluorescence. [Solution] A compound represented by formula (I) or a salt thereof: [In the formula, A represents a ring structure selected from the group consisting of a thiophene ring, a cyclopentene ring, a cyclopentadiene ring, and a furan ring; X represents a C0-C3 alkylene group;Y represents O, S, C(═O)O, or NH,Z represents O, C(Ra) (Rb), Si(Ra) (Rb), Ge(Ra) (Rb), Sn(Ra) (Rb), Se, P(Rc), or P(Rc) (═O) (where Ra and Rb each independently represent a hydrogen atom or an alkyl group, and Rc represents a hydrogen atom, an alkyl group, or an aryl group);R1 and R2 each independently represent from one to three of the same or different substituents selected from the group consisting of a hydrogen atom, a hydroxyl group, a halogen atom, and an alkyl group, a sulfo group, a carboxyl group, an ester group, an amide group, and an azide group each of which may be substituted;R3 represents an acyl residue derived from an amino acid (where the acyl residue is a residue obtained by removing an OH group from a carboxyl group of the amino acid);R4 and R5 each independently represent a hydrogen atom or an alkyl group (where when R4 or R5 is an alkyl group, the R4 or R5, together with R2, may form a ring structure comprising a nitrogen atom to which R4 and R5 are bonded).]
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Paragraph 0086; 0088
(2020/03/28)
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- Multicolor Activatable Raman Probes for Simultaneous Detection of Plural Enzyme Activities
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Raman probes based on alkyne or nitrile tags hold promise for highly multiplexed imaging. However, sensing of enzyme activities with Raman probes is difficult because few mechanisms are available to modulate the vibrational response. Here we present a gen
- Fujioka, Hiroyoshi,Kamiya, Mako,Kojima, Ryosuke,Ozeki, Yasuyuki,Shou, Jingwen,Urano, Yasuteru
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supporting information
p. 20701 - 20707
(2020/12/23)
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- Spontaneously Blinking Fluorophores Based on Nucleophilic Addition/Dissociation of Intracellular Glutathione for Live-Cell Super-resolution Imaging
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Single-molecule localization microscopy (SMLM) allows the reconstruction of super-resolution images but generally requires prior intense laser irradiation and in some cases additives to induce blinking of conventional fluorophores. We previously introduced a spontaneously blinking rhodamine fluorophore based on an intramolecular spirocyclization reaction for live-cell SMLM under physiological conditions. Here, we report a novel principle of spontaneous blinking in living cells, which utilizes reversible ground-state nucleophilic attack of intracellular glutathione (GSH) upon a xanthene fluorophore. Structural optimization afforded two pyronine fluorophores with different colors, both of which exhibit equilibrium (between the fluorescent dissociated form and the nonfluorescent GSH adduct form) and blinking kinetics that enable SMLM of microtubules or mitochondria in living cells. Furthermore, by using spontaneously blinking fluorophores working in the near-infrared (NIR) and green ranges, we succeeded in dual-color live-cell SMLM without the need for optimization of the imaging medium.
- Morozumi, Akihiko,Kamiya, Mako,Uno, Shin-Nosuke,Umezawa, Keitaro,Kojima, Ryosuke,Yoshihara, Toshitada,Tobita, Seiji,Urano, Yasuteru
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supporting information
p. 9625 - 9633
(2020/07/25)
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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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- SUPER-RESOLUTION FLUORESCENT IMAGING PROBE
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[Problem] To provide a novel fluorescent probe for super-resolution imaging that uses fluorescent light emission characteristics that originate from an intermolecular nucleophilic addition-dissociation equilibrium reaction, and to provide a super-resoluti
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-
Paragraph 0133; 0134; 0135; 0136
(2018/03/25)
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- Synthesis of medium-sized aryl-fused nitrogenous heterocycles: Via sequential aryne aza-Claisen rearrangement/ring-closing metathesis
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The reaction of arynes and secondary allylamines furnished ortho-allyl-substituted N-arylanilines via an aza-Claisen rearrangement. In this transformation, the sequential formation of C-C and C-N bonds occurred by involving two aryne molecules under metal
- Rao Mangina,Guduru, Ravinder,Karunakar, Galla V.
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p. 2134 - 2142
(2018/03/26)
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- MANUFACTURING METHOD OF ALKENYLAMINE
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SOLUTION: A manufacturing method of alkenylamine for manufacturing alkenylamine by reacting alkenyl halide and amine, includes conducting the above described reaction in presence of a solution containing alkali metal hydroxide of excess quantity for neutralizing hydrogen halide which is a by-product in the above described reaction, and then separating an oil phase containing generated alkenylamine and a water phase, where unreacted alkali metal hydroxide and alkali metal halide generated by neutralizing hydrogen halide which is a by-product in the above described reaction with alkali metal hydroxide are dissolved, and purifying the resulting oil phase to obtain alkenylamine. EFFECT: Alkenylamine can be manufactured at high yield even with a small used amount of amine to alkenyl halide. SELECTED DRAWING: None COPYRIGHT: (C)2017,JPO&INPIT
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Paragraph 0036
(2017/06/19)
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- A supercritical CO2For vinylsulfonyl reactive disperse dyes and its preparation method and application (by machine translation)
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The invention belongs to the field of dye synthesis, relates to a supercritical CO2 For vinylsulfonyl reactive disperse dyes, and method for preparing the compound. The compounds of this invention with the structure as shown in formula I: type definition of each group in the specification. The compounds have a relatively good dying activity, can be used for the supercritical carbon dioxide, to the wool fiber and polyester fiber has good dyeing properties. (by machine translation)
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Paragraph 0070; 0073
(2017/08/28)
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- Hydrodehalogenation of Haloarenes by a Sodium Hydride–Iodide Composite
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A simple protocol for hydrodebromination and -deiodination of halo(hetero)arenes was enabled by sodium hydride (NaH) in the presence of lithium iodide (LiI). Mechanistic studies showed that an unusual concerted nucleophilic aromatic substitution operates in the present process.
- Ong, Derek Yiren,Tejo, Ciputra,Xu, Kai,Hirao, Hajime,Chiba, Shunsuke
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supporting information
p. 1840 - 1844
(2017/02/05)
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- A general approach to substituted diphenyldiazenes
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A general and practical synthetic method for the construction of unsymmetrically substituted diphenyldiazenes based on classical azo coupling reaction has been developed. A key feature of this method is the use of N,N-diallyl protected aniline derivatives
- Lutz, Toni A.,Spanner, Patrick,Wanner, Klaus T.
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p. 1579 - 1589
(2016/03/01)
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- Synthesis of homoallylic amines and acylhydrazides by tin powder-promoted multicomponent one-pot allylation reactions
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An efficient process for the synthesis of homoallylic amines and N′-homoallylic hydrazides is developed from the one-pot reaction of carbonyl compounds, amines or N-acylhydrazines, allyllic bromide and tin powder using water as solvent. N-Acylhydrazines are found to be more reactive than amines in these processes. They can react not only with aldehydes but also with ketones to give the corresponding N′-homoallylic hydrazides. Copyright
- Ma, Junyan,Huang, Danfeng,Wang, Ke-Hu,Xu, Yanli,Chong, Siying,Su, Yingpeng,Fu, Ying,Hu, Yulai
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p. 571 - 576
(2016/07/16)
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- Facet-Dependent Catalytic Activity of Palladium Nanocrystals in Tsuji-Trost Allylic Amination Reactions with Product Selectivity
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Pd nanocubes, cuboctahedra, and octahedra with good size control were used to catalyze C-N bond formation in the Tsuji-Trost allylic amination reaction of aniline. Nanocubes gave either monoallylaniline or diallylaniline depending on the amount of allyl bromide used, but the octahedra and cuboctahedra only gave mixtures of monoallylaniline and diallylaniline under the same reaction conditions. The Pd nanocubes were stable over multiple cycles of the reaction. The cubes and octahedra were demonstrated to catalyze the amination reaction by using a wide variety of substituted anilines, but the cubes were the best catalyst with consistently the highest efficiency, product yield, and product selectivity. This work demonstrates that the use of metal nanocrystals with proper facet control is important for catalyzing coupling reactions with product selectivity. Getting into shapes: Pd nanocubes, cuboctahedra, and octahedra with good size control are used to catalyze C-N bond formation in the Tsuji-Trost allylic amination reaction of aniline. The Pd nanocube catalyst gives good product selectivity, whereas the Pd octahedra and cuboctahedra catalysts yield mixtures of products under the same reaction conditions. Furthermore, Pd nanocubes are stable over multiple reaction cycles.
- Chanda, Kaushik,Rej, Sourav,Liu, Shu-Ya,Huang, Michael H.
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p. 1813 - 1817
(2015/06/23)
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- One-Pot Synthesis of O-Allylhydroxylamines through the Organocatalytic Oxidation of Tertiary Allylic Amines Followed by a [2,3]-Meisenheimer Rearrangement
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A cheap, green, and highly efficient one-pot method for the synthesis of O-protected allylic alcohols is described. By utilizing 2,2,2-trifluoroacetophenone as the organocatalyst and H2O2 as the oxidant, a variety of allylic amine N-
- Theodorou, Alexis,Limnios, Dimitris,Kokotos, Christoforos G.
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supporting information
p. 5238 - 5241
(2015/03/30)
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- Sequential Oxidative α-Cyanation/Anti-Markovnikov Hydroalkoxylation of Allylamines
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Iron-catalyzed oxidative α-cyanations at tertiary allylamines in the allylic position are followed by anti-Markovnikov additions of alcohols across the vinylic CC double bonds of the initially generated α-amino nitriles. These consecutive reactions generate 2-amino-4-alkoxybutanenitriles from three reactants (allylamines, trimethylsilyl cyanide, and alcohols) in one reaction vessel at ambient temperature.
- Wagner, Alexander,Hampel, Nathalie,Zipse, Hendrik,Ofial, Armin R.
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supporting information
p. 4770 - 4773
(2015/10/12)
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- Monocarboxylate transporter 1 inhibitors as potential anticancer agents
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Potent monocarboxylate transporter 1 inhibitors (MCT1) have been developed based on α-cyano-4-hydroxycinnamic acid template. Structure-activity relationship studies demonstrate that the introduction of p-N, N-dialkyl/diaryl, and o-methoxy groups into cyanocinnamic acid has maximal MCT1 inhibitory activity. Systemic toxicity studies in healthy ICR mice with few potent MCT1 inhibitors indicate normal body weight gains in treated animals. In vivo tumor growth inhibition studies in colorectal adenocarcinoma (WiDr cell line) in nude mice xenograft models establish that compound 27 exhibits single agent activity in inhibiting the tumor growth.
- Gurrapu, Shirisha,Jonnalagadda, Sravan K.,Alam, Mohammad A.,Nelson, Grady L.,Sneve, Mary G.,Drewes, Lester R.,Mereddy, Venkatram R.
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supporting information
p. 558 - 561
(2015/05/27)
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- Equilibrium study of Pd(dba)2 and P(OPh)3 in the Pd-catalyzed allylation of aniline by allyl alcohol
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Reaction of Pd(dba)2 and P(OPh)3 shows a unique equilibrium where the Pd[P(OPh)3]3 complex is favored over both Pd(dba)[P(OPh)3]2 and Pd[P(OPh)3] 4 complexes at room temperature. At a lower temperature, Pd[P(OPh)3]4 becomes the most abundant complex in solution. X-ray studies of Pd[P(OPh)3]3 and Pd(dba)[P(OPh)3]2 complexes show that both complexes have a trigonal geometry with a Pd-P distance of 2.25 A due to the π-acidity of the phosphite ligand. In solution, pure Pd(dba)[P(OPh)3] 2 complex equilibrates to the favored Pd[P(OPh)3] 3 complex, which is the most stable complex of those studied, and also forms the most active catalytic species. This catalyst precursor dissociates one ligand to give the reactive Pd[P(OPh)3]2, which performs an oxidative addition of nonmanipulated allyl alcohol to generate the π-allyl-Pd[P(OPh)3]2 intermediate according to ESI-MS studies.
- Sawadjoon, Supaporn,Orthaber, Andreas,Sjoeberg, Per J. R.,Eriksson, Lars,Samec, Joseph S. M.
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supporting information
p. 249 - 253
(2014/02/14)
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- Metal-free reductive cleavage of C-N and S-N bonds by photoactivated electron transfer from a neutral organic donor
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A photoactivated neutral organic super electron donor cleaves challenging arenesulfonamides derived from dialkylamines at room temperature. It also cleaves a)ArC-NR and b)ArN-C bonds. This study also highlights the assistance given to these cleavage reactions by the groups attached to N in (a) and to C in (b), by lowering LUMO energies and by stabilizing the products of fragmentation. Radical fragmentations: Electron transfer from the photoactivated neutral electron donor 1 delivers high yields of S-N and C-N cleavage products for a range of nitrogen-containing species. These reactions proceed at room temperature and under mild reaction conditions in the absence of any metal reagents. DMF=N,N-dimethylformamide, Ts=4-toluenesulfonyl.
- O'Sullivan, Steven,Doni, Eswararao,Tuttle, Tell,Murphy, John A.
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supporting information
p. 474 - 478
(2014/01/23)
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- Highly selective N-allylation of anilines under microwave irradiation
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An easy and rapid procedure for the preparation of a variety of mono- and bis-allylated anilines via the reaction of allyl bromide with a wide range of anilines under microwave irradiation is described. This approach allows use of mild conditions and short reaction times to give high selectivities and excellent yields.
- Liu, Meiyu,Wang, Xie,Sun, Xiaoliang,He, Wei
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p. 2711 - 2714
(2014/05/06)
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- Nano Pd-Fe3O4@Alg beads: As an efficient and magnetically separable catalyst for Suzuki, Heck and Buchwald-Hartwig coupling reactions
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Catalytic processes are the backbone of many chemical industries. In a comparative study of various heterogeneous catalytic systems, we report efficient and magnetically separable nano Pd-Fe3O4@Alg beads as catalysts for Suzuki, Heck and Buchwald-Hartwig coupling reactions. This catalyst was characterized by SEM, TEM, HRTEM, XRD, EDAX, FT-IR, VSM, DSC-TGA, BET, and UV-Visible spectroscopy. This heterogeneous catalyst showed high catalytic activity and stability for C-C and C-N bond forming coupling reactions with excellent product yield under ligand free conditions. The beads of nano Pd-Fe3O4@Alg can be separated from the reaction mixture by an external magnet and reused for several successive cycles with no appreciable loss in the catalytic activity. The Suzuki and Heck coupling reactions in aqueous medium are greener routes, which is an added advantage of this protocol. This journal is
- Shelkar, Radheshyam S.,Gund, Sitaram H.,Nagarkar, Jayashree M.
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p. 53387 - 53396
(2015/02/05)
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- Mechanistic insights into the Pd-catalyzed direct amination of allyl alcohols: Evidence for an outer-sphere mechanism involving a palladium hydride intermediate
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The mechanism of direct amination of allyl alcohol by a palladium triphenylphosphite complex has been explored. Labelling studies show that the reaction proceeds through a π-allylpalladium intermediate. A second-order dependence of reaction rate on allyl alcohol concentration was observed. Kinetic isotope effect studies and ESI-MS studies are in agreement with a reaction proceeding through a palladium hydride intermediate in which both O-H bond and C-O bond cleavages are involved in rate-determining steps. A stereochemical study supports an outer-sphere nucleophilic attack of the π-allylpalladium intermediate giving complete chiral transfer from starting material to product. Two cleavages: The mechanism of the direct amination of allyl alcohol by palladium complexes bearing triphenylphosphite ligands has been explored. Kinetic isotope and ESI-MS studies are in good agreement with that both Oi£H bond and Ci£O bond cleavages are involved in rate-determining steps. Furthermore, stereochemical studies support an outer-sphere nucleophilic attack of the π-allylpalladium intermediate. Copyright
- Sawadjoon, Supaporn,Sjoeberg, Per J. R.,Orthaber, Andreas,Matsson, Olle,Samec, Joseph S. M.
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supporting information
p. 1520 - 1524
(2014/03/21)
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- PRODUCTION METHOD FOR 2-ALKENYLAMINE COMPOUND
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Provided is a method for producing a 2-alkenylamine compound efficiently and at low cost, using a primary or secondary amine compound and a 2-alkenyl compound as the starting materials therefor. The 2-alkenyleamine compound is produced by 2-alkenylating a primary or secondary amine compound, using a specified 2-alkenylating agent and in the presence of a catalyst comprising a complexing agent and a transition metal precursor stabilized by a monovalent anionic five-membered conjugated diene.
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Paragraph 0049
(2014/07/22)
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- Diallylaminoarenes: A new class of versatile ligands for silver(i) that consistently lead to one-dimensional polymeric metallosupramolecular assemblies
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Ligands comprised of a diallylamino group attached to a phenyl, 2-pyridyl, 2-pyrimidyl, 2-thiazolyl and 2-quinolyl ring react with silver(i) salts (perchlorate and/or triflate) to faithfully assemble into 1-D coordination polymers, regardless of variation
- Kelemu, Solomon W.,Steel, Peter J.
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p. 9064 - 9071
(2013/11/19)
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- Copper-catalyzed electrophilic amination of organolithiums mediated by recoverable siloxane transfer agents
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The development and validation of copper-catalyzed, electrophilic amination of aryl and heteroaryl organolithiums with N,N-dialkyl-O-benzoylhydroxylamines have been achieved exploiting recoverable siloxane transfer agents. Given the ready availability of organolithium compounds, the mild reaction conditions, the ease of product purification, and the ready recovery of the siloxane transfer agents, this transformation comprises a useful tactic to access diverse aryl and heteroaryl amines.
- Nguyen, Minh H.,Smith, Amos B.
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supporting information
p. 4872 - 4875
(2013/10/08)
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- A mild and catalyst-free aromatization using dihydroxylcyclohexanone derivatives as phenyl sources: A new approach to anilines
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A new and efficient protocol for the preparation of N-substituted anilines via an aromatization reaction was developed. 3,5-Dihydroxylcyclohexanone derivatives were used as the sources of the phenyl group and reacted smoothly with primary or secondary amines under mild conditions in the absence of metal catalyst and strong base. A variety of N-substituted anilines were prepared by this method with excellent yields up to 99%. The results indicate that this reaction begins with a nucleophilic addition.
- Luo, Jun,Ji, Enwei,Ye, Jingyuan,Wu, Runze,Qiu, Lei
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p. 4505 - 4508
(2013/08/23)
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- Assisted tandem catalytic RCM-aromatization in the synthesis of pyrroles and furans
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An assisted tandem catalytic transformation of diallyl amines and diallyl ethers into N-aryl pyrroles and furans, respectively, is described. The sequence relies on ring closing metathesis followed by dehydrogenation of the initially formed dihydropyrroles and dihydrofurans. Both steps are Ru-catalyzed, but the sequence requires only one precatalyst, because conversion of the metathesis catalyst into the dehydrogenation catalyst is achieved in situ, triggered by the oxidant tert-butyl hydroperoxide.
- Schmidt, Bernd,Krehl, Stefan,Jablowski, Eric
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supporting information; experimental part
p. 5119 - 5130
(2012/08/07)
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- Pd-catalyzed synthesis of aryl amines via oxidative aromatization of cyclic ketones and amines with molecular oxygen
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Pd-catalyzed intermolecular aerobic dehydrogenative aromatizations have been developed for the arylation of amines with nonaromatic ketones. Under optimized reaction conditions, primary and secondary amines are selectively arylated in good yields with cyclohexanones and 2-cyclohexen-1-ones in the presence of a Pd-catalyst under an atmosphere of molecular oxygen.
- Girard, Simon A.,Knauber, Thomas,Zhou, Feng,Simon, Marc-Olivier,Li, Chao-Jun,Hu, Xiong,Deng, Guo-Jun
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supporting information
p. 5606 - 5609,4
(2012/12/12)
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- Transition-metal-free electrophilic amination of arylboroxines
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A transition-metal-free strategy to construct C(sp2)-N bonds using arylboroxines and O-benzoyl hydroxylamines as coupling partners has been developed. This transformation provides a useful method to access various aromatic amines.
- Xiao, Qing,Tian, Leiming,Tan, Renchang,Xia, Ying,Qiu, Di,Zhang, Yan,Wang, Jianbo
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experimental part
p. 4230 - 4233
(2012/09/22)
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- An atom efficient route to N-aryl and N-alkyl pyrrolines by transition metal catalysis
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The synthesis of N-aryl, N-tosyl, and N-alkyl pyrrolines from allyl alcohols and amines has been developed. The reaction sequence includes a palladium-catalyzed allylation step in which non-manipulated allyl alcohol is used to generate the diallylated amine in good to excellent yield. An excess of allyl alcohol was necessary for efficient diallylation of the amine, where the excess alcohol could be recycled three times. For aryl and tosyl amines, Pd[P(OPh)3]4 was used and for benzyl and alkyl amines a catalytic system comprising Pd(OAc)2, PnBu3, and BEt3 was used. Both the electronic properties and the steric influence of the amine affected the efficiency of the allylation. The isolated diallylated amines were transformed into their corresponding pyrrolines by ring-closing metathesis catalyzed by (H2IMes)(PCy3)Cl 2RuCHPh in good to excellent yield. A one-pot reaction was developed in which aniline was transformed into the corresponding pyrroline without isolating the diallylated intermediate. This one-pot reaction was successfully scaled-up to 1 mL of aniline in which the N-phenyl pyrroline was isolated in 95% yield. The versatility of the reaction in which 3-methyl-1-phenyl pyrroline was prepared in two-steps was demonstrated.
- Sawadjoon, Supaporn,Samec, Joseph S. M.
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experimental part
p. 2548 - 2554
(2011/05/04)
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- Multistep reactions using microreactor chemistry
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A microflow system for the investigation of multistep syntheses involving Pd-catalysed Heck reactions and Ru-catalysed ring-closing metathesis is described. A successful provision of reagent and catalyst delivery in a consecutive fashion allowed control over reaction parameters leading to fast optimisation. The performance of Heck reactions in multistep procedures was not as successful as in the single step coupling, whereas the ring-closing metathesis proved to be successful in the production of the desired compounds for further functionalisation. ARKAT-USA, Inc.
- Ahmed-Omer, Batoul,Barrow, David A.,Wirth, Thomas
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experimental part
p. 26 - 36
(2011/07/07)
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- Sequential combination of ruthenium-, base-, and gold-catalysis - A new approach to the synthesis of medicinally important heterocycles
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A general approach to the high-yielding synthesis of medicinally important heterocycles was achieved through the sequential combination of ring-closing metathesis, base-induced ring opening (BIRO), hydroamination, and a Diels-Alder reaction of functionalized allyl-(2-allylphenyl)amines in the presence of a catalytic amount of Grubbs' second-generation catalyst, base (tBuOK), and [AuCl(PPh3)]/AgOTf. Herein, we also demonstrate the important electronic factors in the BIRO of N-substituted-benzo[b]azepines for the regioselective synthesis of functionalized (Z)-N-substituted-2-(buta-1,3-dienyl) phenylamines in very good yields with high purity; these are very good, useful compounds in medicinal chemistry. We also discovered the selective cascade synthesis of privileged hexahydrophenanthridines from (Z)-N-substituted-2-(buta- 1,3-dienyl)phenylamines by gold catalysis in moderate to good yields with >99 % diastereomeric excess. The possible reaction mechanism for the unusual hydroamination followed by [4+2] cycloaddition of functionalized (Z)-N-substituted-2-(buta-1,3-dienyl)phenylamines through gold catalysis is discussed in this work. A novel process for the synthesis of highly substituted, medicinally important heterocycles was achieved through the sequential combination of ring-closing methathesis, base-induced ring opening, hydroamination, and Diels-Alder reaction of functionalized allyl-(2-allylphenyl) amines in the presence of a catalytic amount of [Ru], base, and [Au] (see scheme). Copyright
- Ramachary, Dhevalapally B.,Narayana, Vidadala V.
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supporting information; experimental part
p. 3514 - 3522
(2011/08/06)
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- Highly efficient and regioselective allylic amination of allylic alcohols catalyzed by [Mo3PdS4] cluster
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A highly efficient and regioselective allylation reaction of amines with allylic alcohols under mild conditions catalyzed by the cubane-type sulfido cluster [(Cp*Mo)3S4Pd(dba)][PF6] with H3BO3 as an additive has been developed. A variety of amines and allylic alcohols are investigated, and in the case of allylic alcohols bearing substituents at either α- or γ-position only linear allylic amination products are obtained.
- Tao, Yinsong,Zhou, Yuhan,Qu, Jingping,Hidai, Masanobu
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experimental part
p. 1982 - 1984
(2010/06/21)
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- Palladium-diphosphine complexes as catalysts for allylations with allyl alcohol
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Several palladium complexes with bidentate phosphine ligands were tested for their activity in the O-allylation of phenols with allyl alcohol. The use of C3-bridged bidentate phosphine ligands results in very high selectivity for O-allylation. The reactions do not require stoichiometric amounts of additives to control the chemoselectivity. Especially, catalysts with gem-dialkyl substituted C3-bridged bidentate phosphine ligands perform very well, resulting in a (equilibrium) conversion of ~50% of phenol with a selectivity of 99% for O-allylation. The use of diallyl ether as the allylating agent results in a significant increase in phenol conversion while maintaining high selectivity for O-allylation. Apart from Pd(OAc)2 as catalyst precursor, Pd(dba)2 was also employed, making it possible to use other types of phosphine or phosphite ligands. With the palladium catalytic system not only phenol, but also aliphatic alcohols can be allylated, as well as aromatic and aliphatic amines.
- Van Rijn, Jimmy A.,Dunnen, Angela Den,Bouwman, Elisabeth,Drent, Eite
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experimental part
p. 96 - 102
(2010/11/18)
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- METHODS OF CHEMICAL SYNTHESIS OF DIAMINOPHENOTHIAZINIUM COMPOUNDS INVOLVING THE USE OF PERSULFATE OXIDANTS
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This invention pertains generally to the field of chemical synthesis and purification, and more specifically to methods of synthesizing and purifying certain 3,7-diamino- phenothiazin-5-ium compounds (referred to herein as "diaminophenothiazinium compound
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Page/Page column 64-65
(2010/12/17)
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- One-pot amide synthesis from allyl or benzyl halides and amines by Pd-catalysed carbonylation
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Amides can be prepared from allyl or benzyl halides and primary or secondary amines, using Pd(0) catalyst under CO pressure, in a one-pot synthesis. The reaction proceeds through the acyl palladium halide formation which undergoes an acylic nucleophilic substitution from the amine.
- Troisi, Luigino,Granito, Catia,Rosato, Francesca,Videtta, Valeria
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experimental part
p. 371 - 373
(2010/03/24)
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- Platinum-catalyzed direct amination of allylic alcohols under mild conditions: Ligand and microwave effects, substrate scope, and mechanistic study
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Transition metal-catalyzed amination of allylic compounds via a π-allylmetal intermediate is a powerful and useful method for synthesizing allylamines. Direct catalytic substitution of allylic alcohols, which forms water as the sole coproduct, has recently attracted attention for its environmental and economical advantages. Here, we describe the development of a versatile direct catalytic amination of both aryl- and alkyl-substituted allylic alcohols with various amines using Pt-Xantphos and Pt-DPEphos catalyst systems, which allows for the selective synthesis of various monoallylamines, such as the biologically active compounds Naftifine and Flunarizine, in good to high yield without need for an activator. The choice of the ligand was crucial toward achieving high catalytic activity, and we demonstrated that not only the large bite-angle but also the linker oxygen atom of the Xantphos and DPEphos ligands was highly important. In addition, microwave heating dramatically affected the catalyst activity and considerably decreased the reaction time compared with conventional heating. Furthermore, several mechanistic investigations, including 1H and 31P{1H} NMR studies; isolation and characterization of several catalytic intermediates, Pt(xantphos)Cl2, Pt(η2-C3H5OH)(xantphos), etc; confirmation of the structure of [Pt(η3-allyl)(xantphos)]OTf by X-ray crystallographic analysis; and crossover experiments, suggested that formation of the π-allylplatinum complex through the elimination of water is an irreversible rate-determining step and that the other processes in the catalytic cycle are reversible, even at room temperature.
- Ohshima, Takashi,Miyamoto, Yoshiki,Ipposhi, Junji,Nakahara, Yasuhito,Utsunomiya, Masaru,Mashima, Kazushi
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supporting information; body text
p. 14317 - 14328
(2010/02/16)
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- Palladium nanoparticle-catalyzed C-N bond formation. A highly regio- and stereoselective allylic amination by allyl acetates
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(Chemical Equation Presented) Palladium nanoparticles, generated in situ from the reaction of palladium(II) chloride, have been demonstrated to be an efficient catalyst for C-N bond formation. A variety of aliphatic and aromatic amines have been allylated by substituted and unsubstituted allyl acetates in high yields by using palladium nanoparticles in the presence of a base without any ligand. The allylations are highly regio- and stereoselective.
- Adak, Laksmikanta,Chattopadhyay, Kalicharan,Ranu, Brindaban C.
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scheme or table
p. 3982 - 3985
(2009/10/17)
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- Sequential aza-Claisen rearrangement and ring-closing metathesis as a route to 1-benzazepine derivatives
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A synthetic strategy based on sequential application of aza-Claisen rearrangement and ring-closing metathesis reaction as key steps has been developed for the synthesis of various 1-benzazepine derivatives of pharmaceutical relevance. Georg Thieme Verlag
- Ghosh, Debalina,Thander, Latibuddin,Ghosh, Sanjay K.,Chattopadhyay, Shital K.
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experimental part
p. 3011 - 3015
(2009/06/27)
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- Direct use of allylic alcohols for platinum-catalyzed monoallylation of amines
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A new direct catalytic amination of allylic alcohols promoted by the combination of platinum and a large bite-angle ligand DPEphos was developed in which the allylic alcohol was effectively converted to a π-allylplatinum intermediate without the use of an activating reagent. The use of the DPEphos ligand was essential for obtaining high catalyst activity and high monoallylation selectivity of primary amines, allowing the formation of a variety of monoallylation products in good to excellent yield.
- Utsunomiya, Masaru,Miyamoto, Yoshiki,Lpposhi, Junji,Ohshima, Takashi,Mashima, Kazushi
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p. 3371 - 3374
(2008/02/12)
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- Mechanistic investigation of the cobalt-catalyzed selective conversion of diallylanilines to quinolines involving C-N and C-H activations
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2,3-Substituted quinolines were readily prepared from diallylanilines in good yields under mild conditions by using Co2(CO)8 as catalyst.1,2 Regioselectivity has been explored by examining a series of electron-donating and electron-withdrawing functional groups at ortho, meta, and para positions of the diallylanilines. The results show that both steric and electronic effects influence the isolated yields. Electron-withdrawing groups inhibit the reaction. Solvent effects, temperature effects, and catalyst loadings have also been investigated. Isotopic labeling experiments were devised to permit delineation of the mechanism of reaction.
- Li, Ng,Jones, William D.
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p. 10707 - 10713
(2008/03/12)
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- Aqueous-mediated N-alkylation of amines
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Direct N-alkylation of primary amines to secondary/tertiary amines and of secondary amines to tertiary amines has been achieved in excellent yields by employing alkyl, benzylic and allylic halides in the presence of NaHCO 3 in an aqueous medium at an elevated temperature. Amines of different stereoelectronic nature react with ease with different halides. The selective formation of secondary amines and the formation of three different substituted tertiary amines are some of the interesting features of this methodology. Reaction in an aqueous medium, operationally convenient conditions, excellent yields and innocuous byproducts, and the absence of transition-metal catalysts, expensive bases, solid supports and the formation of undesired quaternary ammonium salts makes this method a green chemical process. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
- Singh, Chingakham B.,Kavala, Veerababurao,Samal, Akshaya K.,Patel, Bhisma K.
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p. 1369 - 1377
(2008/09/17)
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- Effective monoallylation of anilines catalyzed by supported KF
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Equation Presented A mild and straightforward monoallylation procedure for different anilines is described using the efficient, inexpensive, noncorrosive, and environmentally friendly reagent KF-Celite. By using only a 1/1.2 stoichiometric ratio of electrophilic reagent to aniline, in very short reaction times, the monoallylated products are obtained in high isolated yields via this procedure, which works very effectively regardless of the electronic nature of the substituent on the ring, although electron withdrawing groups make the reactions go even faster.
- Pace, Vittorio,Martinez, Fernando,Fernandez, Maria,Sinisterra, Jose V.,Alcantara, Andres R.
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p. 2661 - 2664
(2008/02/08)
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- Process for the preparation of vinyl- or allyl-containing compounds
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A vinyl- or allyl-containing compound represented by following Formula (3): wherein R2, R3, R4, R5, and R6 each represent hydrogen atom or a nonmetallic atom-containing group; R7 represents a nonmetallic atom-containing group; Y represents a group selected from the group consisting of —Si(R8) (R9) —, —Si(R10) (R11)—O—, the left hand of which is combined with R7, and —NR12—, wherein R8, R9, R10, R11, and R12 each represent hydrogen atom or a nonmetallic atom-containing group; and “n” represents 0 or 1, is prepared by reacting a vinyl or allyl ester compound represented by following Formula (1): wherein R1 represents hydrogen atom or a nonmetallic atom-containing group; R2, R3, R4, R5, R6, and “n” are as defined above, with a compound represented by following Formula (2): [in-line-formulae]R7—Y—H ??(2)[/in-line-formulae] wherein R7 and Y are as defined above, in the presence of a transition element compound.
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Page/Page column 6
(2008/06/13)
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- Direct palladium/carboxylic acid-catalyzed allylation of anilines with allylic alcohols in water
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The direct activation of C-O bonds in allylic alcohols in water as a suspension medium by palladium complexes has been accelerated by carrying out the reactions in the presence of a carboxylic acid. The palladium-catalyzed allylation of anilines using allylic alcohols directly gave allylic anilines in good yields.
- Yang, Shyh-Chyun,Hsu, Yi-Chun,Gan, Kim-Hong
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p. 3949 - 3958
(2007/10/03)
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- A new method for the conversion of allyl alcohol into π-allyl species promoted by nucleophilic interaction with a CO ligand
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Upon treatment with an iridium carbonyl complex, [(PN)Ir(CO)2]+, allyl alcohol can be smoothly converted into π-allyliridium species at ambient temperature via nucleophilic interaction of the alcohol with a CO ligand followed by C(allyl)-O bond cleavage in the resultant protonated allyloxycarbonyl intermediate. The Royal Society of Chemistry 2006.
- Dubs, Christian,Yamamoto, Toshiki,Inagaki, Akiko,Akita, Munetaka
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p. 1962 - 1964
(2008/03/13)
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- SnCl2 mediated efficient N,N-dialkylation of azides to tertiary-amine via potential stannaimine intermediate
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A base free one-pot conversion of azides to N,N-dialkylamine is described. A two-step reaction pathway has been postulated invoking the intermediacy of stannaimine. This new carbon-nitrogen bond formation strategy adds to the repertoire of tin(II) chemistry.
- Roy, Ujjal Kanti,Roy, Sujit
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p. 1525 - 1530
(2007/10/03)
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