62722-94-5

Upstream product

• 504-61-0 (E)-but-2-enol 
• 62-53-3 aniline 
• 69611-44-5 N-(3-methyl-2-butyne)aniline 
• 103204-12-2 1-phenyl-2,5-dihydro-1H-pyrrole 
• 17304-01-7 tricrotylborane 
• 598-32-3 2-hydroxy-3-butene 
• 6117-91-5 (E/Z)-2-buten-1-ol 

Downstream Products

• 4828-94-8 (+/-)-2-(1'-methylallyl)aniline 

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).

Synthetic method of allylamine

The invention provides a synthetic method of allylamine compounds with substituted allyl alcohol and aromatic amines as raw materials through induction of a titanium metal intermediate. The invention relates to a secondary amine substituted by an allyl gr

Synthesis of a leucomitosane via a diastereoselective radical cascade

The preparation of trans-2,3-disubstituted indolines from 1-azido-2-allylbenzene derivatives via a diastereoselective radical cascade using ethyl iodoacetate and triethylborane is described. Further lactamization afforded substituted benzopyrrolizidinones

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.

Synthesis of secondary amines by titanium-mediated transfer of alkenyl groups from alcohols

Reaction of Ti(NMe2)4 with allyl alcohols and primary amines leads to the selective formation of secondary allylic amines. The allyl transfer from the alcohol to the amine occurs with selective allylic transposition. Due to substituent effects in the reactions, we postulate that the reaction occurs through a [2 + 2]/retro-[2 + 2]-cycloaddition mechanism. It was also found that a similar reaction could be accomplished with homoallylic alcohol. In this case, the more complex mechanism leads to the formation of 1-aza-spiro[5.5]undecane. Possible pathways for the homoallylic transfer and cyclization are discussed. Copyright

Allylboration of nitrosobenzene

The allylboration of nitrosobenzene at -70°C resulted in the formation of N- and O-allyl derivatives of N-phenylhydrazine, which were reduced with the second allylborane molecule to N-allylaniline above 100°C.

(π-Allyl)palladium complexes bearing diphosphinidenecyclobutene ligands (DPCB): Highly active catalysts for direct conversion of allylic alcohols

The (π-allyl)palladium complex bearing an sp2-hybridized phosphorus ligand (DPCB-OMe: 1,2-bis(4-methoxyphenyl)-3,4-bis[(2,4,6-tri-tert-butylphenyl)phosphinidene]cyclobutene) efficiently catalyzes direct conversion of allylic alcohols in the absence of activating agents of alcohols such as Lewis acids. N-Allylation of aniline proceeds at room temperature to afford monoallylated anilines in 90-97% yields. C-Allylation of active methylene compounds is also successful at 50 °C using a catalytic amount of pyridine as a base, giving monoallylation products in 85-95% yields. The catalytic mechanism involving hydrido- and (π-allyl)palladium intermediates has been proposed on the basis of stoichiometric examinations using model compounds of presumed intermediates. Copyright

Nitrogen-containing remote functionalised organolithium compounds by reductive opening of five- and six-membered heterocycles

The reaction of different five- or six-membered nitrogen- containing heterocycles such as N-isopropyl-2-phenylpyrrolidine (1), N-phenyl-3-pyrroline (6), N-phenylisoindoline (10), N- phenyltetrahydroisoquinoline (13) and N- methyltetrahydroisoquinoline (19

PLATINUM COMPLEX CATALYZED TRANSFORMATION OF AMINE. N-ALKYLATION AND N-ALLYLATION USING PRIMARY ALCOHOLS

Amines reacted with primary alcohols in the presence of a platinum complex catalyst at 120-180 deg C to give N-alkylated or N-alyllated compounds.