- Silver Salt-Mediated Allylation Reactions Using Allyl Bromides
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A facile, efficient, and chemoselective synthesis of allylic amides has been developed. Allyl bromides were used as the precursors activated by silver triflate. A Ritter-type reaction readily proceeded to give various allyl amides under mild conditions. The reaction protocol was also applicable to different nucleophilic partners to give a wide range of allyl-substituted products in the absence of a base.
- Xiong, Xiaodong,Wong, Jonathan,Yeung, Ying-Yeung
-
supporting information
p. 6974 - 6982
(2021/05/06)
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- A lutidine-promoted photoredox catalytic atom-transfer radical cyclization reaction for the synthesis of 4-bromo-3,3-dialkyl-octahydro-indol-2-ones
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Reported herein is a visible-light-catalyzed photoredox atom-transfer radical cyclization (ATRC) halo-alkylation of 1,6-dienes with α-halo-ketones as the ATRC reagent. This process exhibits high atom economy, high step economy, and high redox economy, which can directly construct a 4-bromo-3,3-dialkyl-octahydro-indol-2-one core under mild conditions in one pot, and lutidine is found to be the key promoter for this ATRC process.
- Zhao, Quan-Sheng,Xu, Guo-Qiang,Xu, Ji-Tao,Wang, Zhu-Yin,Xu, Peng-Fei
-
supporting information
p. 2206 - 2209
(2020/02/26)
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- Metal-organic frameworks containing nitrogen-donor ligands for efficient catalytic organic transformations
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Metal-organic framework (MOFs) compositions based on nitrogen donor-based organic bridging ligands, including ligands based on 1,3-diketimine (NacNac), bipyridines and salicylaldimine, were synthesized and then post-synthetically metalated with metal precursors, such as complexes of first row transition metals. Metal complexes of the organic bridging ligands could also be directly incorporated into the MOFs. The MOFs provide a versatile family of recyclable and reusable single-site solid catalysts for catalyzing a variety of asymmetric organic transformations. The solid catalysts can also be integrated into a flow reactor or a supercritical fluid reactor.
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Page/Page column 69-70
(2020/06/03)
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- Method for preparing allylamine compounds
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The invention discloses a method for preparing allylamine compounds. The allylamine compounds are synthesized by taking an ionic iron (III) complex which has a molecular formula of [(RNCH2CH2NR)CH][FeBr4] (R is tert-butyl) and contains 1,3-di-tert-butyl imidazoline cation as a catalyst, taking di-tert-butyl peroxide as an oxidant and carrying out oxidative coupling reaction on amine compounds andallyl hydrocarbon compounds. The method disclosed by the invention has wide application range, can be used for aromatic amine containing an electron-withdrawing group, is effective for aromatic aminecontaining an electron-donating group, and is a first case of preparing the allylamine compounds through the oxidative coupling reaction of the amine compounds and the allyl hydrocarbon compounds, which is realized by an iron-based catalyst.
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Paragraph 0023
(2018/06/15)
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- Copper-Catalyzed Intramolecular Oxidative Amination of Unactivated Internal Alkenes
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A copper-catalyzed oxidative amination of unactivated internal alkenes has been developed. The Wacker-type oxidative alkene amination reaction is traditionally catalyzed by a palladium through a mechanism involving aminopalladation and β-hydride elimination. Replacing the precious and scarce palladium with a cheap and abundant copper for this transformation has been challenging because of the difficulty associated with the aminocupration of internal alkenes. The combination of a simple copper salt, without additional ligand, as the catalyst and Dess-Martin periodinane as the oxidant, promotes efficiently the oxidative amination of allylic carbamates and ureas bearing di- and trisubstituted alkenes leading to oxazolidinones and imidazolidinones. Preliminary mechanistic studies suggested a hybrid radical-organometallic mechanism involving an amidyl radical cyclization to form the key C-N bond.
- Xiong, Peng,Xu, Fan,Qian, Xiang-Yang,Yohannes, Yared,Song, Jinshuai,Lu, Xin,Xu, Hai-Chao
-
supporting information
p. 4379 - 4383
(2016/03/22)
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- Oxidative amination of benzylic alkanes with nitrobenzene derivatives as nitrogen sources
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The oxidative amination of inert C[sbnd]H bonds has the potential to fundamentally change chemistry but is severely limited by the low chemo- and regio-selectivity under oxidation conditions. Until now, no efficient methodology for the direct intermolecular amination of terminal sp3-C[sbnd]H bonds to N-alkyl amines has existed. Here, a new concept is proposed for the oxidative amination of the terminal sp3-C[sbnd]H bond in alkanes via the construction of a complex reaction system composed of a carbon-supported Co-Ni bimetallic catalyst, an alkane, nitrobenzene, tert-butyl hydroperoxide and hydrogen. This system allows the reduction of nitrobenzene to aniline and the further oxidative amination of the alkane. Nitrobenzene and toluene derivatives can be successfully transformed into the corresponding N-benzyl aniline derivatives with up to 95% isolated yields, and the reaction shows excellent functional group tolerance. This approach offers a new concept for catalyst design and may strongly promote the study of inert C[sbnd]H bond activation and the synthesis of functional N-containing compounds.
- Pang, Shaofeng,Shi, Feng
-
supporting information
p. 5872 - 5876
(2016/12/07)
-
- BIS(PHOSPHINE)-CARBODICARBENE CATALYST COMPLEXES AND METHODS OF USING THE SAME
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An organometallic complex of a tridentate bis(phosphine)-carbodicarbene ligand and a transition metal, is described. In some embodiments the ligand has the structure of Formula (I): The complexes are useful in methods of making an allylic amine carried ou
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Page/Page column 15; 16; 28; 40
(2015/11/09)
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- Intermolecular hydroamination of 1,3-dienes catalyzed by bis(phosphine)carbodicarbene-rhodium complexes
-
A carbodicarbene (CDC)-based pincer ligand scaffold is reported, along with its application to site-selective Rh(I)-catalyzed intermolecular hydroamination of 1,3-dienes with aryl and alkyl amines. To the best of our knowledge, this is the first example of the use of a well-defined CDC complex as an efficient catalyst. Transformations proceed in the presence of 1.0-5.0 mol % Rh complex at 35-120 °C; allylic amines are obtained in up to 97% yield and with >98:2 site selectivity.
- Goldfogel, Matthew J.,Roberts, Courtney C.,Meek, Simon J.
-
supporting information
p. 6227 - 6230
(2014/05/20)
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- N-Bu4NI/TBHP-catalyzed direct amination of allylic and benzylic C(sp3)-H with anilines under metal-free conditions
-
A novel and efficient n-Bu4NI/TBHP-catalyzed direct amination of allylic and benzylic C(sp3)-H with anilines to form N-substituted anilines under metal-free conditions has been developed. the Partner Organisations 2014.
- Zhang, Xusheng,Wang, Min,Li, Pinhua,Wang, Lei
-
supporting information
p. 8006 - 8009
(2014/07/08)
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- Hydrogen-bond-assisted activation of allylic alcohols for palladium-catalyzed coupling reactions
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We report direct activation of allylic alcohols using a hydrogen-bond-assisted palladium catalyst and use this for alkylation and amination reactions. The novel catalyst comprises a palladium complex based on a functionalized monodentate phosphoramidite ligand in combination with urea additives and affords linear alkylated and aminated allylic products selectively. Detailed kinetic analysis show that oxidative addition of the allyl alcohol is the rate-determining step, which is facilitated by hydrogen bonds between the alcohol, the ligand functional group, and the additional urea additive. Hydrogen Bond Rule(s): Direct activation of allylic alcohols and subsequent alkylation and amination reactions are reported. The new catalyst is based on functionalized palladium and phosphoramidite ligands to allow hydrogen bond-assisted activation. Kinetic data are in line with this mechanism as the oxidative addition is the rate-determining step.
- Gumrukcu, Yasemin,Debruin, Bas,Reek, Joost N. H.
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p. 890 - 896
(2014/03/21)
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- N-Alkylation of amines with alcohols over nanosized zeolite beta
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Direct N-alkylation of amines with alcohols was successfully performed by using nanosized zeolite beta, which showed the highest catalytic activity among other conventional zeolites. This method has several advantages, such as eco-friendliness, moderate to high yields, and simple work-up procedure. The catalyst was successfully recovered and reused without significant loss of activity and only water is produced as co-product. In addition, imines were also efficiently prepared from the tandem reactions of amines with 2-, 3- and 4-nitrobenzyl alcohols using nanosized zeolite beta.
- Reddy, Marri Mahender,Kumar, Macharla Arun,Swamy, Peraka,Naresh, Mameda,Srujana, Kodumuri,Satyanarayana, Lanka,Venugopal, Akula,Narender, Nama
-
supporting information
p. 3474 - 3483
(2013/12/04)
-
- 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)
-
- Transition Metal-Catalyzed C-H Amination Using Unactivated Amines
-
One aspect of the invention relates to a method of animation or amidation, comprising the step of combining a substrate, comprising a reactive C—H bond, and an amine or amide, comprising a reactive N—H bond, in the presence of an oxidizing agent and a metal-containing catalyst, thereby forming a product with a covalent bond between the carbon of the reactive C—H bond and the nitrogen of the reactive N—H bond.
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Page/Page column 3; 27
(2011/09/20)
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- Iron/amino acid catalyzed direct N-alkylation of amines with alcohols
-
(Chemical Equation Presented) Ironing it out: The straightforward N-alkylation using alcohols and iron/amino acid catalysis is described (see scheme). The reaction does not proceed by the conventional "borrowing hydrogen" mechanism, but appears to involve a substitution pathway (S N) at the sp3 carbon atom bearing the hydroxy group of the alcohol. Developing a catalyst that is effective at a near neutral pH was key to the successful N-alkylation.
- Zhao, Yingsheng,Foo, Siong Wan,Saito, Susumu
-
supporting information; experimental part
p. 3006 - 3009
(2011/05/04)
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- Platinum-catalyzed direct amination of allylic alcohols under mild conditions: Ligand and microwave effects, substrate scope, and mechanistic study
-
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)
-
- Highly flexible fibre-optic ATR-IR probe for inline reaction monitoring
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Near infrared (IR) applications have considerably profited from the use of flexible and robust fibre-optical probes. So far, a comparable technique for mid-IR was not available due to low stability and lack of robustness of the fibres. We report the use of a newly developed miniaturised diamond ATR-probe with high chemical resistance and pressure resistance based on robust fibre optics. The routine and convenient application in a glove box to highly air- and oxygen-sensitive reactions on a millilitre scale is reported, as well as the monitoring of a solventless reaction on a litre scale.
- Minnich, Clemens B.,Buskens, Pascal,Steffens, H. Christian,Baeuerlein, Patrick S.,Butvina, Leonid N.,Kuepper, Lukas,Leitner, Walter,Liauw, Marcel A.,Greiner, Lasse
-
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- Nucleophilic substitution reactions of alcohols with use of montmorillonite catalysts as solid Bronsted acids
-
(Chemical Equation Presented) We have developed an environmentally benign synthetic approach to nucleophilic substitution reactions of alcohols that minimizes or eliminates the formation of byproducts, resulting in a highly atom-efficient chemical process. Proton- and metal-exchanged montmorillonites (H- and Mn+-mont) were prepared easily by treating Na +-mont with an aqueous solution of hydrogen chloride or metal salt, respectively. The H-mont possessed outstanding catalytic activity for nucleophilic substitution reactions of a variety of alcohols with anilines, because the unique acidity of the H-mont catalyst effectively prevents the neutralization by the basic anilines. In addition, amides, indoles, 1,3-dicarbonyl compounds, and allylsilane act as nucleophiles for the H-mont-catalyzed substitutions of alcohols, which allowed efficient formation of various C-N and C-C bonds. The solid H-mont was reusable without any appreciable loss in its catalytic activity and selectivity. Especially, an Al3+-mont showed high catalytic activity for the α-benzylation of 1,3-dicarbonyl compounds with primary alcohols due to cooperative catalysis between a protonic acid site and a Lewis acidic Al3+ species in its interlayer spaces.
- Motokura, Ken,Nakagiri, Nobuaki,Mizugaki, Tomoo,Ebitani, Kohki,Kaneda, Kiyotomi
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p. 6006 - 6015
(2008/02/10)
-
- A new synthesis of imidazolidin-2-ones via Pd-catalyzed carboamination of N-allylureas
-
A new strategy for the preparation of substituted imidazolidin-2-ones in two steps from readily available N-allylamines is described. Addition of the amine starting materials to isocyanates affords N-allylureas, which are converted to imidazolidin-2-one p
- Fritz, Jonathan A.,Nakhla, Josephine S.,Wolfe, John P.
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p. 2531 - 2534
(2007/10/03)
-
- Hydroamination of 1,3-cyclohexadiene with aryl amines catalyzed with acidic form zeolites
-
The intermolecular hydroamination of 1,3-cyclohexadiene with aniline using zeolite catalysts was investigated. The reaction mechanism and the influence of amine basicity on the rate of reaction were studied. Zeolite H-BEA was the most active catalyst, whereas the incorporation of Zn2+ (Zn/H-BEA) led to decreasing catalytic activity, indicating that the reaction is catalyzed by Bronsted acid sites. Subtle shape selective effects determine the reactivity and selectivity of the zeolites.
- Jimenez, Oriol,Mueller, Thomas E.,Schwieger, Wilhelm,Lercher, Johannes A.
-
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- Efficient C-N bond formations catalyzed by a proton-exchanged montmorillonite as a heterogeneous Bronsted acid
-
Nucleophilic addition of sulfonamides and carboxamides to simple alkenes proceeded smoothly using a proton-exchanged montmorillonite catalyst. The spent catalyst was recovered easily from the reaction mixture and was reusable at least five times without any loss of activity. The unique acidity of the proton-exchanged montmorillonite (H-mont) catalyst was found to be applicable to additional reactions: substitution of hydroxyl groups of alcohols with amides and anilines.
- Motokura, Ken,Nakagiri, Nobuaki,Mori, Kohsuke,Mizugaki, Tomoo,Ebitani, Kohki,Jitsukawa, Koichiro,Kaneda, Kiyotomi
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p. 4617 - 4620
(2007/10/03)
-
- Direct palladium/carboxylic acid-catalyzed allylation of anilines with allylic alcohols in water
-
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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- RUTHENIUM-CATALYZED HYDROAMINATION OF OLEFINS
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Applicants have unexpectedly discovered that catalysts made from a ruthenium catalyst precursor or preformed ruthenium catalysts as otherwise described in the present specification are capable of effecting the addition of a N-H bond across an olefin C=C (olefinic) bond of a substrate with a high degree of regioselectivity and enantioselectivity in high yield. These addition reactions proceed in an anti-Markovnikov or Markovnikov fashion depending upon the catalyst precursor used to generate the ruthenium catalyst which actually participates in the addition reaction. The present invention relates to methods of adding N-H bonds across an olefinic bond in a substrate, using a ruthenium catalyst precursor or catalyst I comprising a compound according to the general structure I: Formula (I) where Ru is a ruthenium atom; L1 represents one or more coordinated ancillary ligands, which may be all the same ligand or which may be a combination of different ligands, each of which may be neutral or formally charged, and each of which may be monodentate and coordinated to ruthenium through a single atom or which may be linked or chelated and bound through more than one atom; L2 represents one or more formally charged ligands which are the same or different and which are optionally susceptible to removal with a strong acid; and x is 0-6, preferably 1, y is 0-6, preferably 2 and n is 1-4, preferably 1.
- -
-
Page/Page column 35; Figure 3
(2010/02/13)
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- Transition metal-catalyzed process for addition of amines to carbon-carbon double bonds
-
The present invention is directed to a process for addition of amines to carbon-carbon double bonds in a substrate, comprising: reacting an amine with a compound containing at least one carbon-carbon double bond in the presence a transition metal catalyst under reaction conditions effective to form a product having a covalent bond between the amine and a carbon atom of the former carbon-carbon double bond. The transition metal catalyst comprises a Group 8 metal and a ligand containing one or more 2-electron donor atoms. The present invention is also directed to enantioselective reactions of amine compounds with compounds containing carbon-carbon double bonds, and a calorimetric assay to evaluate potential catalysts in these reactions.
- -
-
-
- Transition metal-catalyzed process for addition of amines to carbon-carbon double bonds
-
The present invention is directed to a process for addition of amines to carbon-carbon double bonds in a substrate, comprising: reacting an amine with a compound containing at least one carbon-carbon double bond in the presence a transition metal catalyst under reaction conditions effective to form a product having a covalent bond between the amine and a carbon atom of the former carbon-carbon double bond. The transition metal catalyst comprises a Group 8 metal and a ligand containing one or more 2-electron donor atoms. The present invention is also directed to enantioselective reactions of amine compounds with compounds containing carbon-carbon double bonds, and a calorimetric assay to evaluate potential catalysts in these reactions.
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Page column 17; 20
(2008/06/13)
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- (η3-allyl)palladium complexes bearing diphosphinidenecyclobutene ligands: Highly active catalysts for the hydroamination of 1,3-dienes
-
Room-temperature hydroamination of 1,3-dienes with aniline [Eq. (1)] is efficiently catalyzed by cationic η3-allyl palladium complexes, prepared by treating [{(η3-allyl)PdCl)}2] with 1,2-diaryl-3,4-bis[(2,4,6-tri-tert-buty
- Minami,Okamoto,Ikeda,Tanaka,Ozawa,Yoshifuji
-
p. 4501 - 4503
(2007/10/03)
-
- Copper-catalyzed amination of alkenes and ketones by phenylhydroxylamine
-
The catalytic activity of a number of copper complexes and salts toward allylic amination of alkenes using phenylhydroxylamine as the nitrogen fragment donor has been investigated. The best catalyst is CuCl2·2H2O, which produces moderate yields of allylamines with high regioselectivity resulting from double bond transposition. A mechanism similar to that for the molybdenum and the FePc systems is proposed. The first step in the catalytic cycle is the formation of nitrosobenzene from the oxidation of phenylhydroxylamine by Cu(II). The next step is an ene reaction of the alkene with PhNO to produce an allylhydroxylamine, which is then reduced to the allylamine product by Cu(I), thus regenerating Cu(II). The same system can also transfer the nitrogen fragment to the α-carbon of cyclic ketones; this is accompanied by dehydrogenation in some cases to produce α-aminated, α,β-unsaturated ketones.
- Ho,Lau
-
p. 859 - 863
(2007/10/03)
-
- Synthesis of pyrrolidine derivatives by the palladium-catalyzed cyclization of N-(2-cyclohexenyl)bromoacetamide derivatives
-
N-(2-Cyclohexenyl)bromoacetamide derivatives underwent intramolecular cyclization to give pyrrolidine derivatives in the presence of a base and a catalytic amount of palladium catalyst.
- Yang, Shyh-Chyun,Tseng, Fu-Hsiung,Hung, Chung-Wei
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p. 211 - 214
(2007/10/03)
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- Intramolecular cyclization of ortho-(cyclohex-2-enyl)anilines. Modified synthesis of ellipticine
-
It was found that the reactions of arylamines with 3-bromocyclohexene afforded hydrocarbazole compounds in 64-78% yields. A modified procedure for the synthesis of antitumor alkaloid ellipticine was proposed.
- Mustafin,Khalilov,Ismagilov,Baimetov,Spirikhin,Abdrakhmanov,Tolstikov
-
p. 2121 - 2126
(2007/10/03)
-
- INTRAMOLECULAR CYCLIZATION OF ortho-(CYCLOHEX-2-ENYL)ANILINES SYNTHESIS OF ELLIPTICINE
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A convenient method is proposed for the synthesis of the alkaloid ellipticine, which possesses a pronounced antitumoral activity.The interaction of 3-bromocyclohexene (1 equiv.) and 2,5-xylylidine (4 equiv., 150 deg C, 5 h) gave a mixture of hexa- and tetrahydrocarbazoles which was dehydrogenated in the presence of Pd/C to the key synthon 1,4-dimethylcarbazole.The formylation of the carbazole by the Vilsmeier-Haack reaction, interaction with 2,2-diethoxyethylamine, and reduction of the imine formed over Raney nickel led to 3-(2,2-diethoxyethylaminomethyl)-1,4-dimethylcarbazole, the boiling of the N-tosylate of which gave ellipticine in high yield.
- Mustafin, A. G.,Khalilov, I. N.,Tal'vinskii, E. V.,Abdrakhmanov, I. B.,Spirikhin, L. V.,Tolstikov, G. A.
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p. 479 - 483
(2007/10/02)
-
- Reactions of Aryl Azides with Alkenes in the Presence of Aluminium Trichloride. Formation of Novel Aziridines fused to Seven- and Eight-membered Rings
-
Reactions of aryl azides (1) with cyclohexene gave 3-(arylamino)cyclohexenes (2) and trans-1-chloro-2-(arylamino)cyclohexanes (3), whereas that of (1) with cycloheptene or cis-cyclo-octene afforded novel aziridines, 8-aryl-8-azabicyclooctanes (4), or 9-aryl-9-azabicyclononanes (5), respectively.The reaction of phenyl azide (1a) with cis-4-methylpent-2-ene yielded 3-anilino-2-chloro-4-methylpentane (10), but that with the trans-alkene gave 4-anilino-2-methylpent-2-ene (7) and 3-anilino-4-methylpent-1-ene (8).The similar reaction of (1) with 3-trimethylsilylcyclohexene or 3-trimethylsilyl-cis-cyclo-octene produced only (2) or 3-(arylamino)-cis-cyclo-octenes (2').The formation of the aziridines or the ring-opened products was explained by a mechanism via an aziridinium-AlCl3 complex formed from an azide-AlCl3 complex.
- Takeuchi, Hiroshi,Shiobara, Yukihiko,Kawamoto, Hideyuki,Koyama, Kikuhiko
-
p. 321 - 327
(2007/10/02)
-
- Catalytic aminomercuration of olefins in a tandem aminomercuration-deoxymercuration; one-step synthesis of secondary n-arylallylamines from allylalcohols
-
Allyl alcohols react with primary aromatic amines and stoichiometric amounts of mercury(II) tetrafluoroborate to give mixtures of mono- and diallyl anilines. However, the use of the tandem aminomercuration-deoxymercuration promoted by catalytic mercury(II) tetrafluoroborate allows to perform regiospecifically the monoallylation reaction with very high yields. A mechanism is proposed to account for the observed results.
- Barluenga, Jose,Perez-Prieto, Julia,Asensio, Gregorio
-
p. 2453 - 2460
(2007/10/02)
-
- SULFENAMIDES AND SULFINAMIDES IV. HOMOLYSIS OF SULFENAMIDES IN CYCLOHEXENE
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The photocatalysed decomposition of aromatic sulfenamides in cyclohexene is a rapid reaction at ambient temperature.Products fall into two main groups resulting from recombination of initially formed radicals and from intervention of solvent acting as a radical trap.Key words: Aromatic sulfenamides; photolysis; homolysis; free-radicals
- Chan, Christopher L. K.,Duffield, Alan M.,Cole, Edward R.,Southwell-Keely, Peter T.
-
p. 199 - 206
(2007/10/02)
-
- Addition of Phenylnitrenium Ion to Olefins. Reactions of Phenyl Azide with Some Olefins in the Presence of Trifluoroacetic Acid
-
Addition to cyclohexene, cis- or trans-4-methylpent-2-ene, or hex-1-ene of a singlet phenylnitrenium ion, generated from phenyl azide in the presence of trifluoroacetic acid, gave stereo- or regiospecifically N-phenyl-β-hydroxylamines (after work-up with aqueous Na2CO3) via aziridinium ions together with N-allyl and 2- and/or 4-allylanilines.Use of methyl acrylate or methyl crotonate as an electron-deficient olefin led to the formationof N-phenylserine or N-phenylthreonine methyl ester (after work-up with with aqueous Na2CO3), respectively.In the reaction with 1,1-disubstituted ethylene or styrene derivatives, N-substituted anilines were formed through an attack of either tertiary alkyl or benzylic cations on phenyl azide.
- Takeuchi, Hiroshi,Koyama, Kikuhiko,Mitani, Michiharu,Ihara, Rie,Uno, Tomoko,et al.
-
p. 677 - 684
(2007/10/02)
-
- Irradiation of 1,3-Dienes in the Presence of Anilines
-
Acetonitrile solutions of 1,3-cyclohexadiene or 2,5-dimethyl-2,4-hexadiene and aniline, its N-methylated derivatives, Et2NH, or Et3N were irradiated at 350 nm.Adducts (3-anilinoalkenes) were observed in the presence of the primary or secondary anilines but not with the tertiary aniline or the alkylamines.The products are interpreted as arising via an electron-transfer intermediate within the singlet manifold.The cyclic diene gives competitive and dimerization apparently via the triplet.A third diene cyclooctadiene gave no observable chemistry in appreciable amounts.
- Culp, Sandra J.,Bednar, William M.,Pienta, Norbert J.
-
p. 3953 - 3955
(2007/10/02)
-
- Synthesis of Indole Derivatives from N-Alkenyl-o-chloroanilines with Zero-valent Nickel Complex
-
Reaction of N-alkenyl-o-chloroanilines in toluene with tetrakis(triphenylphosphine)nickel(0) was carried out mainly to give indole and indoline derivatives in good yields.A detailed analysis of the reaction products has been done and it allows us to confirm the postulated mechanism of the cyclization reaction.Torsional hindrance around C-C-Csp2 bond seems to prevent the cyclization reaction.
- Rodriguez, J. G.,Canoira, L.
-
p. 883 - 888
(2007/10/02)
-
- A Novel Ring-opening Reaction of an Aziridinium-AlCl3 Complex. Reaction of Phenyl Azide with Alkenes in the Presence of AlCl3
-
Reaction of phenyl azide with alkenes in the presence of ALCl3 gives an aziridinium-AlCl3 complex via an azide-AlCl3 complex; this reaction is followed by ring-opening reactions of the aziridinium-AlCl3 complex to give N-allylanilines and/or N-phenyl-β-chloroamines after work-up with aqueous Na2CO3, but the reaction with cis-cyclo-octene yields a novel aziridine, 9-phenyl-9-azabicyclononane after the work-up.
- Takeuchi, Hiroshi,Shiobara, Yukihiko,Mitani, Michiharu,Koyama, Kikuhiko
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p. 1251 - 1252
(2007/10/02)
-
- Stereospecific Addition of Singlet Phenylnitrenium Ion to Some Alkenes. Reactions of Phenyl Azide with Alkenes in the Presence of Trifluoroacetic Acid
-
Stereospecific addition to some alkenes of a singlet phenylnitrenium ion, generated from phenyl azide in the presence of trifluoroacetic acid, gives aziridinium ions; this addition is followed by ring-opening reactions of aziridinium ions.
- Takeuchi, Hiroshi,Ihara, Rie
-
p. 175 - 177
(2007/10/02)
-