22774-81-8

Upstream product

• 62-53-3 aniline 
• 563-47-3 3-Chloro-2-methylpropene 
• 20443-63-4 3-benzenesulfonyloxy-2-methyl-propene 
• 118793-05-8 [2-Methyl-prop-2-en-(E)-ylidene]-phenyl-amine 
• 513-42-8 3-hydroxy-2-methyl-1-propene 
• 142820-20-0 2-methylallyl methanesulfonate 
• 116-11-0 2-Methoxypropene 
• 100-61-8 N-methylaniline 
• 60700-13-2 N-Trimethylsilyl-N-phenylformamide 
• 513-31-5 2-bromoallyl bromide 

Downstream Products

• 62420-79-5 N-Methallyl-N-phenylthiocarbamidsaeure-O-ethylester 
• 83703-56-4 (2-Methyl-allyl)-((E)-1-methyl-but-2-enyl)-phenyl-amine 
• 910619-00-0 N-phenyl-4-methylpyrrolidine-3-carbaldehyde 
• 910618-98-3 N-phenyl-4-methylpyrrolidine-2-carbaldehyde 
• 106027-38-7 N-phenyl-3-methylpyrrolidine 
• 78286-71-2 2-Methyl-N¹-phenyl-N²-p-tolyl-propane-1,2-diamine 
• 78286-70-1 1,1-dimethyl-N¹,N²-diphenyl-ethanediyldiamine 
• 85692-13-3 4-methyl-N-phenyl-Δ³-pyrroline-2-one 

Relevant academic research and scientific papers

A Simple, Broad-Scope Nickel(0) Precatalyst System for the Direct Amination of Allyl Alcohols

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).

Cp2TiX Complexes for Sustainable Catalysis in Single-Electron Steps

We present a combined electrochemical, kinetic, and synthetic study with a novel and easily accessible class of titanocene catalysts for catalysis in single-electron steps. The tailoring of the electronic properties of our Cp2TiX-catalysts that

Silver-promoted (radio)fluorination of unsaturated carbamates via a radical process

The intramolecular fluorocyclization of unsaturated carbamates is described here using a hypervalent iodine reagent in the presence of a silver catalyst. Both (hetero)aryl-substituted olefins and acrylamides can be utilized as effective substrates. Preliminary mechanistic investigations suggest that the reaction proceeds via a cyclization/1,2-(hetero)aryl migration/fluorination cascade involving an unusual radical process. Furthermore, starting from no-carrier-added [18F]TBAF, a simple one-pot, two-step cascade method was developed for the generation of 18F-labeled heterocycles with high radiochemical purity.

Palladium-catalyzed oxidative arylacetoxylation of alkenes: Synthesis of indole and indoline derivatives

A method for the oxidative arylacetoxylation of alkenes has been developed to synthesize indole and indoline derivatives from readily accessible substrates. The cinnamyl tethered anilines with picolinamide as a directing group provided 3-substituted indoles via intramolecular oxidative arylacetoxylation, and the 2-methyl substituted cinnamyl anilines furnished indoline derivatives with 3-position quaternary stereocenters in good to excellent yields via sequential intramolecular oxidative arylacetoxylation, hydrolysis and oxidation steps.

MANUFACTURING METHOD OF ALKENYLAMINE

SOLUTION: A manufacturing method of alkenylamine for manufacturing alkenylamine by reacting alkenyl halide and amine, includes conducting the above described reaction in presence of a solution containing alkali metal hydroxide of excess quantity for neutralizing hydrogen halide which is a by-product in the above described reaction, and then separating an oil phase containing generated alkenylamine and a water phase, where unreacted alkali metal hydroxide and alkali metal halide generated by neutralizing hydrogen halide which is a by-product in the above described reaction with alkali metal hydroxide are dissolved, and purifying the resulting oil phase to obtain alkenylamine. EFFECT: Alkenylamine can be manufactured at high yield even with a small used amount of amine to alkenyl halide. SELECTED DRAWING: None COPYRIGHT: (C)2017,JPO&INPIT

Aza-Wittig Rearrangements of N-Benzyl and N-Allyl Glycine Methyl Esters. Discovery of a Surprising Cascade Aza-Wittig Rearrangement/Hydroboration Reaction

Treatment of N-(arylmethyl)-N-aryl or N-allyl-N-aryl glycine methyl ester derivatives with nBu2BOTf and iPr2NEt effects an aza-Wittig rearrangement that provides N-aryl phenylalanine methyl ester derivatives and N-aryl allylglycine methyl ester derivatives, respectively, in good yield with moderate to good diastereoselectivity. Under similar conditions, analogous substrates bearing N-carbonyl groups are converted to 1,4,2-oxazaborole derivatives. Additionally, N-allyl-N-aryl glycine methyl ester derivatives subjected to similar conditions at elevated temperatures undergo an aza-[2,3]-Wittig rearrangement, followed by a subsequent hydroboration oxidation reaction, to afford substituted amino alcohol products.

An atom efficient route to N-aryl and N-alkyl pyrrolines by transition metal catalysis

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.

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.

The effective preparation of secondary amines bearing a vinylsilane functionality via the reaction of primary amines with α-chlorine- substituted allylsilanes catalysed by CuCl

The reaction of α-chlorine-substituted allylsilanes with primary amines was promoted by CuCl to result in the selective formation of secondary amines bearing the vinylsilane functionality by a probable SN2′ -allylation keeping the silyl group intact.

Effective monoallylation of anilines catalyzed by supported KF

Equation Presented A mild and straightforward monoallylation procedure for different anilines is described using the efficient, inexpensive, noncorrosive, and environmentally friendly reagent KF-Celite. By using only a 1/1.2 stoichiometric ratio of electrophilic reagent to aniline, in very short reaction times, the monoallylated products are obtained in high isolated yields via this procedure, which works very effectively regardless of the electronic nature of the substituent on the ring, although electron withdrawing groups make the reactions go even faster.