- Palladium-catalyzed aminoallylation of activated olefins with allylic halides and phthalimide
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The three-component aminoallylation reaction of the activated olefins 2 with the phthalimide 1a and allyl chloride proceeded very smoothly in the presence of Pd2dba3·CHCl3 (5 mol %)/P(4-FC6H4)3 (40 mol %) and Cs2CO3 (3 equiv against 2) in dichloromethane at room temperature to give the corresponding aminoallylated products, N-pent-4-enylphthalimides 3, in 58-99% yields. The reaction of oxazolidinone 1b also proceeded very smoothly to give N-(2,2-dicyano-1-phenylpent-4-enyl)-oxazolidinone in a quantitative yield; however, the Tsuji-Trost-type allylation products 4 were obtained in the case of dibenzylamine, N-tosylaniline, and pyrrolidin-2-one. Further, 2 underwent cycloaddition with N-tosylvinylaziridine 9a in the presence of Pd2dba3·CHCl3 (5 mol %)/P(4-FC6H4)3 (40 mol %) in THF at room temperature, giving the corresponding pyrrolidines 11 in 69-99% yields.
- Aoyagi, Kouichi,Nakamura, Hiroyuki,Yamamoto, Yoshinori
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Read Online
- Palladium(0) catalysed allylation reactions with racemic and enantiomerically pure allylic sulfoximines
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Stabilised carbon and nitrogen nucleophiles can be efficiently allylated in a regioselective manner using allylic sulfoximines and palladium(0) catalysis.
- Pyne, Stephen G.,O'Meara, Gareth,David, Dorothy M.
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Read Online
- 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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- Production of allyl compound (by machine translation)
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[Problem] Chlorine contamination risk of the reaction mass, ester reaction agent, and, because the reaction solution cannot be re-used without using dissolved transition metal complex catalyst, metal oxide catalyst obtained by using a relatively simple operation, a relatively high yield or production or synthesis of allyl compounds, and a manufacturing method for a metal oxide catalyst used in the synthesis. [Solution] Allyl alcohol, alcohols, phenol compounds such as allyl group is applied to the dehydration is introduced, allyl ethers, allyl thioether compound such as allyl compounds such as allyl manufacturing method, and an alcohol, the compound is mixed in the liquid, at least one of titania and zirconia obtained by mixing molybdenum compound, titania and/or zirconia on the surface of the molybdenum oxide film formed using the metal oxide catalyst. Figure 1 [drawing] (by machine translation)
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Paragraph 0046; 0068; 0069
(2019/07/17)
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- C-N Bond Formation from Allylic Alcohols via Cooperative Nickel and Titanium Catalysis
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Amination of allylic alcohols is facilitated via cooperative catalysis. Catalytic Ti(O-i-Pr)4 is shown to dramatically increase the rate of nickel-catalyzed allylic amination, and mechanistic experiments confirm activation of the allylic alcohol by titanium. Aminations of primary and secondary allylic alcohols are demonstrated with a variety of amine nucleophiles. Diene-containing substrates also cyclize onto the nickel allyl intermediate prior to amination, generating carbocyclic amine products. This tandem process is only achieved under our cooperative catalytic system.
- Nazari, S. Hadi,Tiempos-Flores, Norma,Forson, Kelton G.,Bourdeau, Jefferson E.,Michaelis, David J.
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p. 10646 - 10654
(2018/09/06)
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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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- Direct use of allylic alcohols and allylic amines in palladium-catalyzed allylic amination
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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)
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- Green and Scalable Palladium-on-Carbon-Catalyzed Tsuji–Trost Coupling Reaction Using an Efficient and Continuous Flow System
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The first continuous flow Tsuji–Trost coupling reaction between allylic compounds and various nucleophiles has been successfully achieved within only around 40 s during a single pass through a cartridge filled with palladium on carbon (Pd/C). Two methods have been designed by using the H-cube ThalesNano technology that enable the efficient production of added-value compounds on the gram scale with high productivity. Under the optimized conditions, the cartridge catalyst can be used for 60 min of continuous processing without a decrease in reactivity. A large range of substrates and nucleophiles have successfully been submitted to the standard methods, giving good-to-excellent yields and productivity.
- Cazorla, Clément,Billamboz, Muriel,Bricout, Hervé,Monflier, Eric,Len, Christophe
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p. 1078 - 1085
(2017/02/23)
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- Direct Allylic Amination of Allylic Alcohol Catalyzed by Palladium Complex Bearing Phosphine-Borane Ligand
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The direct electrophilic, nucleophilic, and amphiphilic allylations of allylic alcohol by use of a palladium catalyst and organometallic reagents such as organoborane and organozinc has been developed. The phosphine-borane compound works as the effective ligand for palladium-catalyzed direct allylic amination of allylic alcohol. Thus, with secondary amines, the reaction was completed in only 1 h, even at room temperature.
- Hirata, Goki,Satomura, Hideaki,Kumagae, Hidenobu,Shimizu, Aika,Onodera, Gen,Kimura, Masanari
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supporting information
p. 6148 - 6151
(2017/11/24)
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- Cs2CO3-Promoted Direct N-Alkylation: Highly Chemoselective Synthesis of N-Alkylated Benzylamines and Anilines
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Herein is described an efficient and chemoselective method for the synthesis of diversely substituted secondary amines in yields up to 98 %. Direct mono-N-alkylation of primary benzylamines and anilines with a wide range of alkyl halides is promoted by a cesium base in the absence of any additive or catalyst. The basicity and solubility of cesium carbonate in anhydrous N,N-dimethylformamide not only enables mono-N-alkylation of primary amines but also suppresses undesired dialkylation of the desired amines.
- Castillo, Juan-Carlos,Orrego-Hernández, Jessica,Portilla, Jaime
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p. 3824 - 3835
(2016/08/20)
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- Sodium Perborate: A Facile Catalyst for Allylation of Active Centers
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An efficient and ecofriendly allylation of O-H, N-H, and C-H groups has been achieved successfully with the reaction of allyl bromide by using sodium perborate as a new catalyst in aqueous media. The advantage of this method is operationally simple, short reaction time, good yield, and simple workup conditions over the previously reported conventional methods such as amination, oxyalkylation reactions of allyl bromide, and Friedel-Crafts allylation chemistry.
- Jayaprakash, Soora Harinath,Krishna, Balam Satheesh,Prasad, Sthanikam Siva,Sudha, Sarva Santhi,Reddy, Cirandur Suresh
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supporting information
p. 355 - 362
(2015/10/29)
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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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- Pentacoordinated Carboxylate π-Allyl Nickel Complexes as Key Intermediates for the Ni-Catalyzed Direct Amination of Allylic Alcohols
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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
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supporting information
p. 14571 - 14578
(2015/10/05)
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- Palladium-catalyzed direct amination of allylic alcohols at room temperature
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A palladium complex ligated with Xantphos has beenz identified as an efficient catalyst for the catalytic amination of allylic alcohols, which allows the direct amination of allylic alcohols with amines to proceed at room temperature in the absence of additives. The method 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 with high stereoselectivities.
- Wang, Maorong,Xie, Yinjun,Li, Jiawen,Huang, Hanmin
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supporting information
p. 2781 - 2786
(2015/01/08)
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- C-N bond cleavage of allylic amines via hydrogen bond activation with alcohol solvents in Pd-catalyzed allylic alkylation of carbonyl compounds
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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
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supporting information; experimental part
p. 19354 - 19357
(2012/01/06)
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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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- Gold-catalyzed intermolecular markovnikov hydroamination of allenes with secondary amines
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A cationic (CAAC)gold(I) complex promotes the addition of all types of nontertiary amines to a variety of alienes, affording allylic amines in good to excellent yields; the amino fragment always adds to the less substituted terminus of the CCC skeleton.
- Xiaoming, Zeng,Soleilhavoup, Michele,Bertrand, Guy
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scheme or table
p. 3166 - 3169
(2009/11/30)
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- GOLD CATALYZED HYDROAMINATION OF ALKYNES AND ALLENES
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Methods are provided for the catalytic hydroamination of compounds having an alkyne or allene functional group, in which the compound is contacted with ammonia or an amine in the presence of a catalytic amount of a gold complex under conditions sufficient for hydroamination to occur.
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Page/Page column 42; 10/13
(2010/01/29)
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- Amination of allylic alcohols in water at room temperature
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The "trick" to carrying out regiocontrolled aminations of allylic alcohols in water as the only medium is use of a nanomicelle's interior as the organic reaction solvent. When HCO2Me is present, along with the proper base and source of catalytic Pd, allylic amines are cleanly formed at room temperature.
- Nishikata, Takashi,Lipshutz, Bruce H.
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supporting information; experimental part
p. 2377 - 2379
(2009/12/01)
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- Allyl sulfides are privileged substrates in aqueous cross-metathesis: Application to site-selective protein modification
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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)
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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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- Ruthenium-Catalyzed Chemoselective N-Allyl Cleavage: Novel Grubbs Carbene Mediated Deprotection of Allylic Amines
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A novel application of the Grubbs carbene complex has been discovered. The first examples of the catalytic deprotection of allylic amines with reagents other than palladium catalysts have been achieved through Grubbs carbene mediated reaction. Significantly, the catalytic system directs the reaction toward the selective deprotection of allylic amines (secondary as well as tertiary) in the presence of allylic ethers. A variety of substrates, including enantiomerically pure multifunctional piperidines, are also usable. The new method is more convenient, chemoselective, and operationally simple than the palladium-catalyzed method. The current mechanistic hypothesis invokes a nitrogen-assisted ruthenium-catalyzed isomerization, followed by hydrolysis of the enamine intermediate. We believe that the reactive species involved in the reaction may be an Ru-H species rather than the Grubbs carbene itself. Thus, the isomerization may occur according to the hydride mechanism. The synthetic utility of this ruthenium-catalyzed allyl cleavage is illustrated by the preparation of indolizidine-type alkaloids.
- Alcaide, Benito,Almendros, Pedro,Alonso, Jose M.
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p. 5793 - 5799
(2007/10/03)
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- Facile removal strategy for allyl and allyloxycarbonyl protecting groups using solid-supported barbituric acid under palladium catalysis
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Solid-supported barbituric acid can be used for the palladium(0)-catalyzed deprotection of allyl amines, carbamates, carbonates, esters and ethers. This solid-supported reagent facilitates isolation and purification of the deprotected compounds, especially acids and amines.
- Tsukamoto, Hirokazu,Suzuki, Takamichi,Kondo, Yoshinori
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p. 1105 - 1108
(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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- A novel use of Grubbs' carbene. Application to the catalytic deprotection of tertiary allylamines
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Figure presented The first examples accounting for the catalytic deprotection of allylic amines by using reagents different from palladium catalysts have been achieved via Grubbs' carbene-mediated reaction. The current mechanistic hypothesis invokes a nitrogen-assisted ruthenium-catalyzed isomerization, followed by hydrolysis of the enamine intermediate. We believe that an unprecedented mode of ring opening of the ruthena-cyclobutane was involved.
- Alcaide, Benito,Almendros, Pedro,Alonso, Jose M.,Aly, Moustafa F.
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p. 3781 - 3784
(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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- 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
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p. 1515 - 1530
(2007/10/02)
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- The Pyrolysis of N-Allyl Compounds: Free-radical and Retro-ene Mechanisms
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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
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p. 2247 - 2273
(2007/10/02)
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