- Preparation method of medical intermediate N-BOC-3-pyrroline
-
The invention discloses a preparation method of a medical intermediate N-BOC-3-pyrroline. The method comprises the following steps: adding a proper amount of benzylamine, 3-bromopropylene, dichloromethane and an alkaline reagent into a reaction bottle for reaction to obtain an enamine compound; dissolving the enamine compound in dichloromethane, adding a catalyst (Grubbs first generation) for reaction, adding anhydrous sodium sulfate after adding water for layering, and performing suction filtration to obtain mother liquor; adding 1-chloroethyl chloroformate and methanol into the mother liquor, debenzylating to obtain pink solid, adding petroleum ether into the pink solid, pulping, and carrying out suction filtration to obtain 3-pyrroline hydrochloride; and re-dissolving the 3-pyrroline hydrochloride with water, adding an alkaline solution of NaHCO3 and (BOC)2O, stirring and reacting, extracting after the reaction is finished, separating out an organic phase, and drying to obtain a finished product of N-BOC-3-pyrroline. The method is low in raw material cost, simple in process step, high in yield, small in pollution, high in product purity and suitable for industrial production.
- -
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Paragraph 0065-0066; 0069-0070; 0073-0074
(2021/07/31)
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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
-
supporting information
p. 287 - 292
(2019/02/12)
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- A Simple, Broad-Scope Nickel(0) Precatalyst System for the Direct Amination of Allyl Alcohols
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The preparation of allylic amines is traditionally accomplished by reactions of amines with reactive electrophiles, such as allylic halides, sulfonates, or oxyphosphonium species; such methods involve hazardous reagents, generate stoichiometric waste streams, and often suffer from side reactions (such as overalkylation). We report here the first broad-scope nickel-catalysed direct amination of allyl alcohols: An inexpensive NiII/Zn couple enables the allylation of primary, secondary, and electron-deficient amines without the need for glove-box techniques. Under mild conditions, primary and secondary aliphatic amines react smoothly with a range of allyl alcohols, giving secondary and tertiary amines efficiently. This “totally catalytic” method can also be applied to electron-deficient nitrogen nucleophiles; the practicality of the process was demonstrated in an efficient, gram-scale preparation of the calcium antagonist drug substance flunarizine (Sibelium).
- Sweeney, Joseph B.,Ball, Anthony K.,Lawrence, Philippa A.,Sinclair, Mackenzie C.,Smith, Luke J.
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supporting information
p. 10202 - 10206
(2018/08/06)
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- COMPOUNDS OF PHOSPHINANES AND AZAPHOSPHINANES, A PROCESS FOR THEIR PREPARATION AND PHARMACEUTICAL COMPOSITIONS CONTAINING THEM
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Compounds of formula (I) wherein: Ak1 represents an alkyl chain, X represents —(CH2)m—, —CH(R)—, —N(R)—, —CH2—N(R)—, —N(R)—CH2— or —CH2—N(R)—CH2—, m and R are as defined in the description, R1 and R2 each represent H when X represents —(CH2)m—, —CH(R)—, —N(R)—, —CH2—N(R)— or —N(R)—CH2—, or together form a bond when X represents —CH2—N(R)—CH2—, R3 represents NH2, Cy-NH2, Cy-Ak3-NH2 or piperidin-4-yl, Cy and Ak3 are as defined in the description, R4 and R5, which may be identical or different, each represent H or F, their optical isomers, and addition salts thereof with a pharmaceutically acceptable acid. Medicinal products containing the same which are useful in treating conditions requiring a TAFIa inhibitor.
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-
Paragraph 1898; 1899; 1900
(2018/02/27)
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- Direct use of allylic alcohols and allylic amines in palladium-catalyzed allylic amination
-
Allylic alcohols and allylic amines were directly utilized in a Pd-catalyzed hydrogen-bond-activated allylic amination under mild reaction conditions in the absence of any additives. The cooperative action of a Pd-catalyst and a hydrogen-bonding solvent is most likely responsible for its high reactivity. The catalytic system is compatible with a variety of functional groups and can be used to prepare a wide range of linear allylic amines in good to excellent yields. Furthermore, this methodology can be easily applied to the one-step synthesis of two drugs, cinnarizine and naftifine, on a gram scale.
- Jing, Jiangyan,Huo, Xiaohong,Shen, Jiefeng,Fu, Jingke,Meng, Qinghua,Zhang, Wanbin
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supporting information
p. 5151 - 5154
(2017/07/12)
-
- Pentacoordinated Carboxylate π-Allyl Nickel Complexes as Key Intermediates for the Ni-Catalyzed Direct Amination of Allylic Alcohols
-
Direct amination of allylic alcohols with primary and secondary amines catalyzed by a system made of [Ni(1,5-cyclooctadiene)2] and 1,1′-bis(diphenylphosphino)ferrocene was effectively enhanced by adding nBu4NOAc and molecular sieves, affording the corresponding allyl amines in high yield with high monoallylation selectivity for primary amines and high regioselectivity for monosubstituted allylic alcohols. Such remarkable additive effects of nBu4NOAc were elucidated by isolating and characterizing some nickel complexes, manifesting the key role of a charge neutral pentacoordinated η3-allyl acetate complex in the present system, in contrast to usual cationic tetracoordinated complexes earlier reported in allylic substitution reactions.
- Kita, Yusuke,Sakaguchi, Hironobu,Hoshimoto, Yoichi,Nakauchi, Daisuke,Nakahara, Yasuhito,Carpentier, Jean-Fran?ois,Ogoshi, Sensuke,Mashima, Kazushi
-
supporting information
p. 14571 - 14578
(2015/10/05)
-
- Sequential Oxidative α-Cyanation/Anti-Markovnikov Hydroalkoxylation of Allylamines
-
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.
-
supporting information
p. 4770 - 4773
(2015/10/12)
-
- 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
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p. 620 - 632
(2014/01/17)
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- Phosphane-pyridine iron complexes: Synthesis, characterization and application in reductive amination through the hydrosilylation reaction
-
A series of 6 cyclopentadienyl phosphanyl-pyridine piano-stool iron complexes was prepared in good yields, characterized, and studied in the catalytic reductive amination of benzaldehyde derivatives through hydrosilylation reactions by using polymethylhydrosiloxane as the hydrosilane source and in dimethylcarbonate as the solvent at 40 °C. Single-crystal X-ray structural analyses were performed for all the complexes. A series of 6 cyclopentadienyl phosphanyl-pyridine piano-stool iron complexes was prepared, characterized, and studied in the catalytic reductive amination of benzaldehyde derivatives in dimethylcarbonate through hydrosilylation reactions by using polymethylhydrosiloxane as the hydrosilane source. Copyright
- Jaafar, Hassen,Li, Haoquan,Misal Castro, Luis C.,Zheng, Jianxia,Roisnel, Thierry,Dorcet, Vincent,Sortais, Jean-Baptiste,Darcel, Christophe
-
experimental part
p. 3546 - 3550
(2012/10/18)
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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.
-
experimental part
p. 2548 - 2554
(2011/05/04)
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- Allylic amination using well-defined [(NHC)Pd(?3-allyl)Cl] complexes and PPh3
-
The allylic amination reaction catalyzed by [(NHC)Pd(allyl)-Cl] complexes has been studied, and the presence of PPh3found to be essential for the catalytic system to be active. [(1-Mesityl-3-methylimidazol-2-ylidene)Pd(?3- C3H5)Cl] hasbeen used to optimize the conditions of the reaction with (E)-1,3-diphenylprop-3-enyl acetate and benzylamine under bi-phasic conditions (aqueous base/CH2Cl2). The best yields ofisolated product (98%) were obtained using aqueous 1 MK2CO3. The influence of the NHC ligand and the allyl frag-ment on the pre-catalyst was also examined. Two new neu-tral [(NHC)Pd(?3-1-RC3H4)Cl] complexes [NHC = 1-mesityl-3-methylimidazol-2-ylidene or 1-(2,6- diisopropylphenyl)-3-methylimidazol-2-ylidene; R = H or Ph] have been preparedand a decrease of the reaction time observed with the former. NMR studies have shown that this pre-catalyst is more easilyactivated than its ?3-allyl analogue and that the predominantactivation pathway involves attack of the amine at the allyl fragment. This reaction occurs exclusively in the presence ofPPh3, thus suggesting that cationic [(NHC)Pd(allyl)(PPh3)] +complexes, which are more electrophilic, are formed in situand allow the amine to react with the allyl fragment. A tetra-fluoroborate cationic complex has therefore been preparedfrom [(NHC)Pd(allyl)Cl], PPh3, and AgBF4 and fully charac-terized. This complex is an active pre-catalyst in the allylicamination reaction. The scope of the reaction was examinedunder the optimized reaction conditions with several dif-ferent nitrogen nucleophiles and allylic acetates. The amin-ation products were obtained in yields ranging from 73 to 98%, except for that from cyclohexenyl acetate and diben-zylamine. Finally, the reaction performed directly with theallylic alcohol and benzylamine led to a mixture of allylicamines in 9% yield. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009.
- Roland, Sylvain,Cotet, William,Mangeney, Pierre
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experimental part
p. 1796 - 1805
(2009/09/06)
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- Palladium nanoparticle-catalyzed C-N bond formation. A highly regio- and stereoselective allylic amination by allyl acetates
-
(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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- Highly chemoselective metal-free reduction of tertiary amides
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This communication describes the chemoselective metal-free reduction of tertiary amides to the corresponding amines. Hantzsch ester is used as a mild reducing agent for the reduction of trifluoromethanesulfonic anhydride activated amides providing the tertiary amines with high functional group tolerance. Copyright
- Barbe, Guillaume,Charette, Andre B.
-
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- Allyl sulfides are privileged substrates in aqueous cross-metathesis: Application to site-selective protein modification
-
Allyl sulfides undergo efficient cross-metathesis in aqueous media with Hoveyda-Grubbs second generation catalyst 1. The high reactivity of allyl sulfides in cross-metathesis was exploited in the first examples of cross-metathesis on a protein surface. S-Allylcysteine was incorporated chemically into the protein, providing the requisite allyl sulfide handle. Preliminary efforts to genetically incorporate S-allylcysteine into proteins are also reported. Copyright
- Lin, Yuya A.,Chalker, Justin M.,Floyd, Nicola,Bernardes, Goncalo J. L.,Davis, Benjamin G.
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supporting information; experimental part
p. 9642 - 9643
(2009/02/04)
-
- Process for the preparation of vinyl- or allyl-containing compounds
-
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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- Asymmetric hydroformylation of vinyl acetate: Application in the synthesis of optically active isoxazolines and imidazoles
-
Equation Presented (R)- and (S)-2-(Acetyloxy)-propanal were prepared [93.8% ee, 102 b/l for (R), 96.9% ee, 149 b/l for (S)] via asymmetric hydroformylation of vinyl acetate on a 150-180 g scale and were used as the starting materials in the synthesis of chiral isoxazoline and imidazole derivatives which proceeded without racemization of the chiral center.
- Thomas,Axtell, Alex T.,Klosin, Jerzy,Wei, Peng,Rand, Cynthia L.,Clark, Thomas P.,Landis, Clark R.,Abboud, Khalil A.
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p. 2665 - 2668
(2008/02/09)
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- Oligomeric benzylsulfonium salts: Facile benzylation via high-load ROMP reagents
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(Chemical Equation Presented) The development of high-load, oligomeric benzylsulfonium salts, generated via ring-opening metathesis polymerization, and their utility in facile benzylations of various nucleophiles is reported. These oligomeric sulfonium salts exist as free-flowing powders and are stable at room temperature. After the benzylation event, purification is attained via simple dry load/filtration, followed by solvent removal to deliver products in excellent yield and purity.
- Zhang, Mianji,Flynn, Daniel L.,Hanson, Paul R.
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p. 3194 - 3198
(2008/02/04)
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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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- METHOD FOR PRODUCING ALLYLAMINES
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PROBLEM TO BE SOLVED: To provide a method for obtaining allylamines from allyl alcohols and amines at a low cost without using CO2. SOLUTION: The method for producing the allylamines represented by formula (3): R3-CH=CH-CHR4-NR1R2 (wherein, R1 and R2 mean each a hydrogen atom, an alkyl group, an aryl group or an arylalkyl group; and R3 and R4 mean each a hydrogen atom, an alkyl group, an aryl group or an arylalkyl group) is carried out as follows. The amines represented by formula (1): R1-NH-R2 are reacted with the allyl alcohols represented by formula (2): R3-CH=CH-CHR4-OH in the presence of a water-soluble palladium complex in a two-phase solvent of water and a water-insoluble organic solvent.
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Page/Page column 7
(2008/06/13)
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- Diphosphines of dppf-type incorporating electron-withdrawing furyl moieties substantially improve the palladium-catalysed amination of allyl acetates
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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
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p. 1198 - 1202
(2007/10/03)
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- Use of a bulky phosphine of weak σ-donicity with palladium as a versatile and highly-active catalytic system: Allylation and arylation coupling reactions at 10-1-10-4 mol% catalyst loadings of ferrocenyl bis(difurylphosphine)/Pd
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Carbon-carbon(sp2-sp2 and sp1-sp 2) and carbon-nitrogen (nucleophilic allylation) coupling processes are promoted by a catalytic system containing [PdCl(η3-C 3H5)]2 with the new ferrocenyl bis(difurylphosphine) 1,1′-bis[di(5-methyl-2-furyl)phosphino]ferrocene, Fc[P(FuMe)2]2. Starting from aryl bromides or allylic acetates this versatile catalyst system may be used at low palladium loadings (10-1-10-4 mol%) in some Heck, Suzuki, Sonogashira and allylic amination reactions to give cross-coupled products in excellent yield. Remarkably high activity is obtained in allylic substitution reactions, providing a significant impetus for the development of bulky phosphines possessing weak σ-donicity for this particular reaction.
- Hierso, Jean-Cyrille,Fihri, Aziz,Amardeil, Régine,Meunier, Philippe,Doucet, Henri,Santelli, Maurice
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p. 9759 - 9766
(2007/10/03)
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- Water enables direct use of allyl alcohol for Tsuji-Trost reaction without activators
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(Chemical Equation Presented) An aqueous biphasic reaction system enables the direct use of allyl alcohol in the Tsuji-Trost reaction without the help of any activating reagents for allyl alcohol. The reaction conditions are neutral to basic, allowing the use of amines as the nucleophile. Theoretical calculations have elucidated the importance of hydration of the hydroxy group for the smooth generation of π-allylpalladium species.
- Kinoshita, Hidenori,Shinokubo, Hiroshi,Oshima, Koichiro
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p. 4085 - 4088
(2007/10/03)
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- Cycloisomerization promoted by the combination of a ruthenium-carbene catalyst and trimethylsilyl vinyl ether, and its application in the synthesis of heterocyclic compounds: 3-Methylene-2,3-dihydroindoles and 3-methylene-2,3- dihydrobenzofurans
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Substituted N and O heterocycles have been synthesized by the cycloisomerization of dienes using a ruthenium-carbene catalyst. The products obtained with and without trimethylsilyl vinyl ether differ (see scheme, Cy = cyclohexyl, Mes = 2,4,6-trimethylphenyl, Ts = p-toluenesulfonyl).
- Terada, Yukiyoshi,Arisawa, Mitsuhiro,Nishida, Atsushi
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p. 4063 - 4067
(2007/10/03)
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- Pd·Et3B-catalyzed alkylation of amines with allylic alcohols
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A combination of catalytic amounts of Pd (0.05 mmol) and Et3B (0.3 mmol) promotes allylic alkylation of primary and secondary aromatic and aliphatic amines (1.0 mmol) by the direct use of allylic alcohols, providing tertiary amines in excellent yields under mild conditions (room temperature ~ 50°C).
- Kimura, Masanari,Futamata, Makoto,Shibata, Kazufumi,Tamaru, Yoshinao
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p. 234 - 235
(2007/10/03)
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- Palladium-tetraphosphine catalysed allylic substitution in water
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The cis,cis,cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane/[PdCl (C3H5)]2 system catalyses allylic amination in water with very high substrate/catalyst ratio in good yields. A turnover number of 980 000 can be obtained for the addition of dipropylamine to allyl acetate in the presence of this catalyst.
- Feuerstein, Marie,Laurenti, Dorothée,Doucet, Henri,Santelli, Maurice
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p. 2313 - 2315
(2007/10/03)
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- Palladium-tetraphosphine complex: An efficient catalyst for allylic substitution and Suzuki cross-coupling
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A new tetraphosphine, the cis-cis-cis-1,2,3,4-tetrakis (diphenylphosphinomethyl)cyclopentane (Tedicyp) has been synthesized and used in palladium-catalyzed reactions. This tetraphosphine in combination with [Pd(C3H5)Cl]2 affords a very efficient catalyst for coupling reactions. Turnover numbers of 980 000 for allylic amination, 9 800 000 for allylic alkylation and 97 000 000 for Suzuki cross-coupling can be obtained in the presence of this catalyst.
- Feuerstein,Laurenti,Doucet,Santelli
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p. 2320 - 2326
(2007/10/03)
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- Dramatic acceleration of the catalytic process of the amination of allyl acetates in the presence of a tetraphosphine/palladium system
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The cis,cis,cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane/ [PdCl(C3H5)]2 system catalyses allylic amination in good yields with a very high substrate/catalyst ratio; a turnover number of 680 000 and a turnover frequency of 8125 h-1 can be obtained for the addition of dipropylamine to allyl acetate in the presence of this catalyst.
- Feuerstein,Laurenti,Doucet,Santelli
-
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- Aminomethylation of functionalized organozinc reagents and grignard reagents using immonium trifluoroacetates
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New immonium trifluoroacetates 1 and 2 react readily with functionalized organozinc or magnesium reagents leading to the corresponding aminomethylated products of type 5 and 7. The resulting bis-allylamines were deallylated leading to primary amines.
- Millot, Nicolas,Piazza, Claudia,Avolio, Salvatore,Knochel, Paul
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p. 941 - 948
(2007/10/03)
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- Phenyl chloro(thionoformate): A new dealkylating agent of tertiary amines
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Phenyl chloro(thionoformate) reacts rapidly with unhindered tertiary aliphatic amines at 20° to give a thiocarbamate and an alkyl chloride. Dialkylcyclohexylamines react surprisingly rapidly to form predominantly cyclohexene. The thiocarbamates are converted into the secondary amine salt by treatment with dimethyl sulfate, followed by hydrolysis with water. Rates of reaction and alkyl group cleavage selectivity in amines were found to be superior or comparable to those previously reported with chloroformates.
- Milan, David S.,Prager, Rolf H.
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p. 841 - 849
(2007/10/03)
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- Zinc Mediated Allylation of Azides: A Novel Method for the High Yield Preparation of N-Allylamines
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A quick and efficient approach for mono N-allylamines has been developed by the reaction of allyl zinc reagent with alkyl and aryl azides in DMF. - Keywords: azides; zinc; DMF; allylamine
- Kumar, H. M. Samapath,Anjaneyulu, S.,Reddy, B. V. Subba,Yadav, J. S.
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p. 551 - 552
(2007/10/03)
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- Mono and diphosphine borane complexes grafted on polypyrrole matrix: Direct use as supported ligands for Rh and Pd catalysis
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A new versatile method for the synthesis of supported mono and diphosphines on polypyrrole matrix is described, based on the protective borane complexation of the phosphorus atom. For the first time, the unknown alkylation of a diphosphine ethano bridge, was obtained with near yield close to 70%, leading to its derivative 8 bearing the polymerizable pyrrole group on a side chain. The different supported mono and diphosphine boranes 12-15 have been applied with success in palladium-catalyzed allylation, cross-coupling reaction and in rhodium-catalyzed hydrogenation. It is of particular interest that supported phosphine boranes can be used without previous decomplexation, forming in situ the catalytically active species from Pd(OAc)2 or RhCl3. Moreover, the recoverable polymer could be used again in rhodium-catalyzed hydrogenation with a very good efficiency after several turn-overs. Nethertheless, we may point out that with palladium catalysis, the addition of Pd(dba)2 was necessary to recover the catalytic activity. These results demonstrate that the phosphine borane complexes are key precursors for the synthesis of functionalized mono and diphosphines, and for their direct use in generating catalysts.
- Riegel, Nadege,Darcel, Christophe,Stephan, Olivier,Juge, Sylvain
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p. 219 - 233
(2007/10/03)
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- Palladium-Catalyzed Allylic Amination of Allylic Alcohols with Tin(II) Chloride and Triethylamine
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Allylic alcohols caused allylic amination with primary or secondary amines in the presence of a catalytic amount of Pd(PPh3)4 and stoichiometric amount of tin(II) chloride in THF at 50 deg C to produce the corresponding allylic amines regioselectively.
- Masuyama, Yoshiro,Kagawa, Masaaki,Kurusu, Yasuhiko
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p. 1121 - 1122
(2007/10/03)
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- ?-Allyl palladium methodology for selective deprotection of allylamines. Practical synthesis of secondary amines
-
The palladium-promoted deallylation of allylamines derived from primary and secondary amines is achieved with high to quantitative yield in the presence of 2-mercaptobenzoic acid as an allyl scavenger.This method was used for the sequential cleavage of diallylamines.A synthetic application of this procedure is presented in the preparation of secondary amines from diallylamines. - Keywords: allylamine; deallylation; sequential deprotection; ?-allyl palladium complexes; 2-mercaptobenzoic acid; substitution of amines
- Lemarie-Audoire, Sandrine,Savignac, Monique,Dupuis, Christophe,Genet, Jean Pierre
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p. 1157 - 1166
(2007/10/03)
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- Role of the macrocyclic polyether in the synthesis of N-alkylcarbamate ester from primary amines, CO2 and alkyl halides in the presence of crown-ethers
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Primary amines, RNH2 1, and CO2 easily afford monoalkylammonium N-alkylcarbamates, [RNH3][O2CNHR] 2, that have been reacted with alkyl halides, R'X, in the presence of crown-ethers to give organic carbamates in good yield. We report here the synthesis and spectroscopic characterization of some alkylammonium carbamates 2, where R - benzyl 2a, allyl 2b, ter-butyl 2c, cyclohexyl 2d, and discuss their stability in solution and the conditions in which they can react with alkyl halides to give organic carbamates, RNHC(O)OR'. The role played by the macrocyclic ligand in modifying the reactivity of monoalkylammonium carbamates 2 towards R'X has been rationalized and the influence of parameters such as solvent, temperature and CO2 pressure on the yield and selectivity of the process leading to organic carbamates has been also settled.
- Aresta,Quaranta
-
p. 1515 - 1530
(2007/10/02)
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- A Convenient Synthesis of Substituted Piperazines via Aminomercuration-Demercuration of Diallylamines
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cis- and trans-2,6-Bispiperazines (II) which bear equal or different substituents at each nitrogen are obtained in the reaction of N-substituted diallylamines with mercury(II) acetate and arylamines followed by a double decomposition process with potassium bromide.Their reduction with sodium borohydride lead to the corresponding 1,4-disubstituted cis- and trans-2,6-dimethylpiperazines III.Steric factors account for the remarkable stereoselectivity observed in the preparation of compounds IIIi-IIIn in which a 3:1 cis to trans ratio is found.
- Barluenga, J.,Najera, C.,Yus, M.
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p. 917 - 921
(2007/10/02)
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