- Hydrosilylation of nitrogen-containing organic compounds: Model studies
-
1,1,3,3-tetramethyldisiloxane (M2H) was used as the hydrosilylating agent for nitrogen-containing alkene derivatives: N-allylaniline (Naa), N-allylcyclohexylamine (Nach), N-allylpiperidine (Nap), 4-vinylpyridine (4VP) and 2-vinylpyri
- Chechelska-Noworyta, Aleksandra,Owińska,Hasik, Magdalena
-
-
Read Online
- Controlling the Coordination Sphere of Alkyllithiums Results in Selective Reactions with Allylic Amines
-
Described herein is a selective way to control the reaction of allylic amines with metalorganic bases depending on the amine handle as well as the metalorganic base is used. Depending on the number of coordinating groups within the amine handle either a selective carbometalation or deprotonation reaction can be performed. By changing the alkali metal within the base from lithium to either sodium or potassium, a change of chemoselectivity takes place and the reaction of piperidinoallylamine can be controlled.
- Kroesen, Ulrike,Unkelbach, Christian,Schildbach, Daniel,Strohmann, Carsten
-
-
Read Online
- Allylic Substitution using Heterogeneous Palladium Catalysts
-
Allylic substitution of the acetoxy group of allylic acetates by various nucleophiles is catalysed by heterogeneous palladium catalysts in the presence of triphenylphosphine.
- Bergbreiter, David E.,Chen, Bushi
-
-
Read Online
- Solvent interactions in the allylation of piperidine
-
The reaction between allylbromide and piperidine has been studied in different protic and aprotic solvents. The reaction is first order with respect to [allylbromide] and [piperidine]. A correlation analysis of the rate data with solvent properties shows that polarity (Y ), polarizability (P), and electrophilicity (E) of the solvent simultaneously influence the rate of reaction. From the regression analysis, information regarding the relative solvation of the reactants and the activated complex is obtained and a solvation model is proposed.
- Devender,Manikyamba
-
-
Read Online
- Diphosphines of dppf-type incorporating electron-withdrawing furyl moieties substantially improve the palladium-catalysed amination of allyl acetates
-
Highly active Pd/diphosphine catalytic systems incorporating new, air-stable ferrocenyl-furylphosphines allow nucleophilic allylic amination at room temperature with unprecedented turnover frequencies. For instance, in the presence of 0.01 mol % catalyst the coupling of aniline to allyl acetate occurs at a TOF of more than 10,000 h-1; even the addition of the less nucleophile morpholine to allyl acetate is observed with a TOF of 4250 h -1. The amination of the sterically demanding geranyl acetate, a monoterpene derivative of interest in the flavour industry, at low catalyst loadings demonstrates the scope of this methodology, which provides in addition noticeable advantages in terms of economical (resource- and energy-saving) and sustainable chemistry (high selectivity, no additive, low metal content, and thus easier purification).
- Fihri, Aziz,Hierso, Jean-Cyrille,Vion, Anthony,Duc, Hanh Nguyen,Urrutigoity, Martine,Kalck, Philippe,Amardeil, Regine,Meunier, Philippe
-
-
Read Online
- Photochemical Activation of Tertiary Amines for Applications in Studying Cell Physiology
-
Representative tertiary amines were linked to the 8-cyano-7-hydroxyquinolinyl (CyHQ) photoremovable protecting group (PPG) to create photoactivatable forms suitable for use in studying cell physiology. The photoactivation of tamoxifen and 4-hydroxytamoxifen, which can be used to activate Cre recombinase and CRISPR-Cas9 gene editing, demonstrated that highly efficient release of bioactive molecules could be achieved through one- and two-photon excitation (1PE and 2PE). CyHQ-protected anilines underwent a photoaza-Claisen rearrangement instead of releasing amines. Time-resolved spectroscopic studies revealed that photorelease of the tertiary amines was extremely fast, occurring from a singlet excited state of CyHQ on the 70 ps time scale.
- Asad, Naeem,Deodato, Davide,Lan, Xin,Widegren, Magnus B.,Phillips, David Lee,Du, Lili,Dore, Timothy M.
-
supporting information
p. 12591 - 12600
(2017/09/23)
-
- Silica-functionalized CuI: An efficient and selective catalyst for N-benzylation, allylation, and alkylation of primary and secondary amines in water
-
Silica-functionalized CuI has been reported as an efficient and selective catalyst for the selective mono-N- and N,N-dibenzylation, allylation, and alkylation of primary amines with benzylic, allylic, and alkyl halides using NaOH as base in aqueous medium. By changing the reaction temperature, mono- or di-benzylation, allylation, or alkylation could be achieved in good yield and selectivity. Secondary amines have also been benzylated, allylated, and alkylated under similar conditions. SiO2-CuI has been characterized by Fourier transform-infrared, atomic absorption spectrometry, thermalgravimetric analysis, X-ray diffraction, scanning electron microscopy, and transmission electron microscopy, and found to be highly selective and recyclable under the reaction conditions. [Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications for the following free supplemental resource(s): Full experimental and spectral details.] Copyright
- Shamim, Tahira,Kumar, Vineet,Paul, Satya
-
p. 620 - 632
(2014/01/17)
-
- Tsuji-trost N-allylation with allylic acetates by using a cellulose-palladium catalyst
-
Allylic amines were synthesized by a simple procedure using a biodegradable and easily recyclable heterogeneous cellulose-Pd catalyst through N-allylation of primary and secondary amines. The scope of this protocol includes aliphatic and benzylamines with substituted and unsubstituted allyl acetates and culminates in high yield syntheses. The highlights of the protocol include a ligand-free reaction, simple workup, and catalyst recyclability. Allylic amines were synthesized by N-allylation of primary and secondary amines through a simple and easy procedure involving the use of a heterogeneous cellulose-Pd catalyst; aliphatic and benzylamines underwent facile reaction with substituted and unsubstituted allyl acetates in high yields. Copyright
- Vaddula, Buchi Reddy,Saha, Amit,Varma, Rajender S.,Leazer, John
-
supporting information
p. 6707 - 6709
(2013/01/15)
-
- C-N bond cleavage of allylic amines via hydrogen bond activation with alcohol solvents in Pd-catalyzed allylic alkylation of carbonyl compounds
-
Hydrogen-bond-activated C-N bond cleavage of allylic amines was realized in Pd-catalyzed allylic alkylation to form the C-C bond product. The method could be expanded to a series of allylic amines and carbonyl compounds with excellent results. It provides a new and convenient access to C-C bond formation based on Pd-catalyzed allylic alkylation of allylic amines by using only inexpensive alcohol solvents.
- Zhao, Xiaohu,Liu, Delong,Guo, Hui,Liu, Yangang,Zhang, Wanbin
-
supporting information; experimental part
p. 19354 - 19357
(2012/01/06)
-
- The Pauson-Khand reaction: A gas-phase and solution-phase examination using electrospray ionization mass spectrometry
-
A series of dicobalt hexacarbonyl complexes with charged alkyne ligands were prepared to enable the study of the Pauson-Khand reaction using ESI-MS. The hexacarbonyl complexes can be activated in the gas phase through removal of a CO ligand. The resulting pentacarbonyl ions react readily with alkenes, and no discrimination between alkenes was found for this step, indicating that alkene association is not rate determining in the intermolecular reaction. Solution-phase ESI-MS studies on a system set up for intramolecular reactivity revealed only the hexacarbonyl complex as a detectable intermediate, and the reaction was shown to have a large enthalpy and entropy of activation, consistent with ligand dissociation being rate limiting in the reaction.
- Henderson, Matthew A.,Luo, Jingwei,Oliver, Allen,McIndoe, J. Scott
-
experimental part
p. 5471 - 5479
(2011/12/13)
-
- Stereoselective isomerisation of N-Allyl aziridines into geometrically stable Z enamines by using rhodium hydride catalysis
-
In the presence of rhodium(I) hydride catalysts, tertiary N-allylamines are known to isomerise into E enamines. In contrast, we have recently found that N-allylaziridines isomerise to form Z enamines. On the basis of literature data, the most likely mecha
- Tsang, Derek S.,Yang, Sharon,Alphonse, France-Aimee,Yudin, Andrei K.
-
p. 886 - 894
(2008/09/21)
-
- Cascade reactions: A new synthesis of 2-benzofuran-2-ylacetamides by sequential Pd(0)-catalyzed deallylation-Pd(II)-catalyzed aminocarbonylative heterocyclization of 1-(2-allyloxyaryl)-2-yn-1-ols
-
(Chemical Equation Presented) A general and efficient synthesis of 2-benzofuran-2-ylacetamides 5 starting from 1-(2-allyloxyaryl)-2-yn-l-ols 1, amines 4, and CO, in the presence of catalytic amounts of PdI2 in conjunction with PPh3 and KI, has been developed based on the "sequential homobimetallic catalysis" concept, that is, a process in which two different complexes of the same metal, but in two different oxidation states, promote two catalytic cycles in sequence. The first cycle corresponds to a Pd(0)-catalyzed aminodeallylation of 1 with formation of the free phenol 2, which then undergoes Pd(II)-catalyzed aminocarbonylative heterocyclization to give the final product 5.
- Gabriele, Bartolo,Mancuso, Raffaella,Salerno, Giuseppe,Costa, Mirco
-
p. 9278 - 9282
(2008/03/14)
-
- Catalysis with palladium colloids supported in poly(acrylic acid)-grafted polyethylene and polystyrene
-
Grafts of poly(acrylic acid) on polyethylene powder (PE-g-PAA) or polystyrene (PS-g-PAA) can be used to support Pd(O) crystallites that function like a homogeneous Pd(O) catalyst in some reactions. These Pd-PE-g-PAA catalysts were active in allylic substitution reactions in the presence of added phosphine ligand. A catalyst analogous to the Pd-PE-g-PAA powder catalyst on polystyrene (Pd-PS-g-PAA) was similarly active for allylic substitution and could also be used in Heck reactions at 80-100°C in N,N-dimethylacetamide (DMA). Analysis of the product solutions for Pd leachate and a correlation of the Pd leaching with product formation in the allylic substitution chemistry for both types of catalysts suggests that the active catalysts in these reactions are leached from the support. In the case of the allylic substitution reaction, external triphenylphosphine and substrate together are required for the chemistry and Pd leaching.
- Bergbreiter, David E.,Kippenberger, Andrew,Zhong, Zhenqi
-
p. 1343 - 1350
(2007/10/03)
-
- Montmorillonite clay-catalysed synthesis of cyclic allylamines
-
A mild and efficient catalytic method for the synthesis of cyclic N-allylamines using an acid-exchanged montmorillonite as a catalyst is described.
- Hachemaoui, A?cha,Belbachir, Mohammed
-
p. 124 - 125
(2007/10/03)
-
- Synthesis of pharmacologically relevant indoles with amine side chains via tandem hydroformylation/fischer indole synthesis
-
The sequence of hydroformylation and Fischer indole synthesis starting from amino olefins and aryl hydrazines is described. In a convergent manner, the two units bearing pharmacologically relevant substituents are assembled in the final indolization step. This modular and diversity-oriented approach to tryptamines and homotryptamines can be conducted in water and allows synthesis of branched and nonbranched tryptamines as well as tryptamine-based pharmaceuticals such as the 5-HT1D agonist L 775 606.
- Schmidt, Axel M.,Eilbracht, Peter
-
p. 5528 - 5535
(2007/10/03)
-
- Soluble polymer-supported synthesis of tertiary amines
-
The synthesis of tertiary amines on a modified soluble polymer, poly(ethylene glycol) (PEG), is described. The PEG-bound quaternary intermediates were assembled via Michael addition reaction, followed by alkylation. Cleavage from the soluble polymer support was induced by insoluble weak basic resin, to afford the target tertiary amines in excellent purity.
- Chen, Zuxing,Yang, Guichun,Zhang, Zhaojun
-
p. 729 - 734
(2007/10/03)
-
- Isoxazoline fibrinogen receptor antagonists
-
This invention relates to novel isoxazolines and isoxazoles of formula (I): or a pharmaceutically acceptable salt or prodrug form thereof. The invention relates to novel isoxazolines which are useful as antagonists of the platelet glycoprotein IIb/IIIa fibrinogen receptor complex, to pharmaceutical compositions containing such compounds, processes for preparing such compounds, and to methods of using these compounds, alone or in combination with other therapeutic agents, for the inhibition of platelet aggregation, as thrombolytics, and/or for the treatment of thromboembolic disorders.
- -
-
-
- Efficient coupling reactions of allylamines with soft nucleophiles using nickel-based catalysts
-
Substitution reactions of N,N-diethylallylamine 1 with soft nucleophiles such as active methylene compounds 2a-c and piperidine 5 proceed much more rapidly in the presence of Ni(dppb)2 [dppb = 1,4-bis(diphenylphosphino)butane] as catalyst than with comparable palladium systems.
- Bricout, Herve,Carpentier, Jean-Francois,Mortreux, Andre
-
p. 1393 - 1394
(2007/10/03)
-
- Polyethylene-Bound Soluble Recoverable Palladium(0) Catalysts
-
The use of diphenylphosphine-terminated ethylene oligomers as ligands for palladium(0) and palladium(II) is described.With use of these polymeric ligands, it is possible to carry out homogeneous reactions characteristic of (Ph3P)4Pd and (Ph3P)2Pd(OAc)2 with essentially complete recovery of the Pd catalyst.The only limitation to repeated reuse of the catalyst is its immolative catalytic oxidation of the phosphine ligand by adventitious oxygen.
- Bergbreiter, David E.,Weatherford, David A.
-
p. 2726 - 2730
(2007/10/02)
-
- N-Alkylation d'amines en catalyse homogene. Synthese de mono- et de diamines cycliques
-
Ruthenium compounds are appropriate catalysts in the N-alkylation of amines.The synthesis of N-alkylated cyclic amines from a cyclic amine and an alcohol or via the condensation between a diol and a primary amine are described.The reaction with cyclic amines is highly selective, especially in the presence of a phosphine, making it a high yielding preparative procedure.The catalytic condensation between cyclic amines and diols yields either an aminoalcohol (A) or a bicyclic diamine (B).The temperature, the presence of phosphine, and the ratio of amine to diol are decisive in directing the reaction toward A or B.The proposed mechanism involves the dehydrogenation of the alcohol followed by attack of the amine on the aldehyde intermediate.
- Bitsi, G.,Schleiffer, E.,Antoni, F.,Jenner, G.
-
p. 343 - 352
(2007/10/02)
-
- A New Method of α-Functionalization for Tertiary Amines by Nucleophilic Substitution of α-Siloxy Amines
-
α-Siloxy amines, which were easily prepared by "silicon Polonovski reaction" of tertiary amine N-oxides with trialkylsilyl trifluoromethanesulfonate, were treated with various nucleophiles to give the corresponding α-functionalized tertiary amines in moderate to good yields.This new method has to the advantage that it enables the α-substitution of amines not only by alkyl groups but also by alkenyl and aryl groups with sp2 carbon as a reaction center, since the introduction of such groups is difficult in electrophilic substitution of dipole-stabilized α-lithio amines.Besides the organometallics such as Grignard and organoaluminum reagents, trimethylsilyl cyanide and silyl enol ether could also be employed as nucleophiles in the presence of an appropriate Lewis acid.
- Tokitoh, Norihiro,Okazaki, Renji
-
p. 735 - 740
(2007/10/02)
-
- TRANSFORMATION OF ALLYLSILANES INTO ALLYLAMINES VIA PHENYLTELLURINYLATION
-
Allylsilanes were treated with benzenetellurinyl trifluoracetate below room temperature followed by amines at 65 deg.C in 1,2-dichloroethane in the presence of boron trifluoride etherate, readily giving allylamines.
- Hu, Nan X.,Aso, Yoshio,Otsubo, Tetsuo,Ogura, Fumio
-
p. 4949 - 4952
(2007/10/02)
-
- Palladium/Polystyrene Catalysts
-
The reaction of reactive alkali metal organometallic derivatives of divinylbenzene-cross-linked polystyrene with solutions of dichloro(1,5-cyclooctadiene)palladium(II) to form palladium/polystyrene catalysts is described.Organometallic polymers used in these reactions include polystyryllithium, polystyrylbenzyllithium, polystyrylphenyl(trimethylsilyl)methyllithium and polystyrene-bound sodium anthracene.The palladium/polystyrene catalysts formed in these reactions were characterized by ESCA and electron microscopy, and their activity as hydrogenation catalysts was examined in various solvents and under various conditions of catalyst pretreatment.Comparisons of the catalytic activity of these catalysts to commercial Pd/C in the hydrogenation of various substrates are also made .Novel catalytic activity observed from these palladium/polystyrene catalysts includes some activity as decarbonylation catalysts in reactions with simple alkyl and aryl aldehydes and their use in place of tetrakis(triphenylphosphine)palladium(0) as a catalyst for the formation of tertiary allylamines from allyl esters and secondary amines.The interaction of functional groups such as organolithium and carboxylic acid groups attached to the polystyrene support with the active centers of hydrogenation catalysts was also demonstrated by their effect on the activity of these hydrogenation catalysts.
- Bergbreiter, David E.,Chen, Bushi,Lynch, Thomas J.
-
p. 4179 - 4186
(2007/10/02)
-
- The Pyrolysis of N-Allyl Compounds: Free-radical and Retro-ene Mechanisms
-
Flash vacuum pyrolysis of N-alkyl-N-allylanilines gives imines by free radical cleavage of the allyl group followed by loss of an atom (or group of atoms) from the α-carbon atom of the alkyl group.The corresponding N-propargyl derivatives also give imines on pyrolysis, but the mechanism is a concerted retro-ene process which may lead to different products from the corresponding N-allyl compound.N-Allyl-N,N-dialkylamines also decompose thermally by a retro-ene process
- Cadogan, J. I. G.,Hickson, Clare L.,McNab, Hamish
-
p. 2247 - 2273
(2007/10/02)
-
- STUDIES ON HETEROCYCLIC QUATERNARY NITROGEN BASES: KINETICS OF TRANSALKYLATION OF PRIMARY AMINES BY N-SUBSTITUTED 5,6-DIHYDRO-2,4-DIPHENYLNAPHTHOPYRIDINIUM CATIONS
-
N-substituents in 5,6-dihydro-2,4-diphenylnaphthopyridiniums are transferred to piperidine by unimolecular and / or bimolecular processes in chlorobenzene solution.The kinetics of this reaction at variable temperatures were studied.It has been shown that the reaction follows either SN1 or SN2 mechanisms dependant on the nature of N-substituent.
- Elshafie, Sayed Mahmoud M.
-
p. 525 - 528
(2007/10/02)
-
- UNIMOLECULAR AND BIMOLECULAR TRANSFER OF N-SUBSTITUENTS FROM PYRIDINIUM CATIONS: EVIDENCE FOR A CLEAR MECHANISTIC CHANGEOVER
-
N-Substituents in 2,4,6-triphenylpyridiniums are transferred to piperidine, morpholine and pyridine by unimolecular and/or bimolecular processes in chlorobenzene solution.These processes are quite distinct and afford no evidence for a mechanism intermediate between SN1 and SN2.
- Katritzky, Alan R.,Musumarra, Giuseppe,Sakizadeh, Kumars,El-Shafie, Sayed M. M.,Jovanovic, Bratislav
-
p. 2697 - 2699
(2007/10/02)
-
