22014-91-1Relevant articles and documents
Palladium-catalyzed aminoallylation of activated olefins with allylic halides and phthalimide
Aoyagi, Kouichi,Nakamura, Hiroyuki,Yamamoto, Yoshinori
, p. 5977 - 5980 (2002)
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.
Palladium(0) catalysed allylation reactions with racemic and enantiomerically pure allylic sulfoximines
Pyne, Stephen G.,O'Meara, Gareth,David, Dorothy M.
, p. 3623 - 3626 (1997)
Stabilised carbon and nitrogen nucleophiles can be efficiently allylated in a regioselective manner using allylic sulfoximines and palladium(0) catalysis.
Dehydrative Allylation of Amine with Allyl Alcohol by Titanium Oxide Supported Molybdenum Oxide Catalyst
Kon, Yoshihiro,Nakashima, Takuya,Fujitani, Tadahiro,Murayama, Toru,Ueda, Wataru
supporting information, p. 287 - 292 (2019/02/12)
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.
Production of allyl compound (by machine translation)
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Paragraph 0046; 0068; 0069, (2019/07/17)
[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)
C-N Bond Formation from Allylic Alcohols via Cooperative Nickel and Titanium Catalysis
Nazari, S. Hadi,Tiempos-Flores, Norma,Forson, Kelton G.,Bourdeau, Jefferson E.,Michaelis, David J.
, p. 10646 - 10654 (2018/09/06)
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.
A Simple, Broad-Scope Nickel(0) Precatalyst System for the Direct Amination of Allyl Alcohols
Sweeney, Joseph B.,Ball, Anthony K.,Lawrence, Philippa A.,Sinclair, Mackenzie C.,Smith, Luke J.
supporting information, p. 10202 - 10206 (2018/08/06)
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).
Direct Allylic Amination of Allylic Alcohol Catalyzed by Palladium Complex Bearing Phosphine-Borane Ligand
Hirata, Goki,Satomura, Hideaki,Kumagae, Hidenobu,Shimizu, Aika,Onodera, Gen,Kimura, Masanari
supporting information, p. 6148 - 6151 (2017/11/24)
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.
Direct use of allylic alcohols and allylic amines in palladium-catalyzed allylic amination
Jing, Jiangyan,Huo, Xiaohong,Shen, Jiefeng,Fu, Jingke,Meng, Qinghua,Zhang, Wanbin
supporting information, p. 5151 - 5154 (2017/07/12)
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.
Green and Scalable Palladium-on-Carbon-Catalyzed Tsuji–Trost Coupling Reaction Using an Efficient and Continuous Flow System
Cazorla, Clément,Billamboz, Muriel,Bricout, Hervé,Monflier, Eric,Len, Christophe
, p. 1078 - 1085 (2017/02/23)
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.
Cs2CO3-Promoted Direct N-Alkylation: Highly Chemoselective Synthesis of N-Alkylated Benzylamines and Anilines
Castillo, Juan-Carlos,Orrego-Hernández, Jessica,Portilla, Jaime
, p. 3824 - 3835 (2016/08/20)
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.
