72641-03-3

Upstream product

• 106625-69-8 ethyl (E)-3-phenyl-2-propenyl carbonate 
• 100-01-6 4-nitro-aniline 
• 673-32-5 1-Phenylprop-1-yne 
• 4407-36-7 (2E)-3-phenyl-2-propen-1-ol 
• 4393-06-0 1-Phenyl-2-propen-1-ol 
• 86537-61-3 ethyl cinnamylcarbonate 
• 104-54-1 3-Phenylpropenol 
• 14371-10-9 (E)-3-phenylpropenal 

Relevant academic research and scientific papers

Hydrogen-bond-assisted activation of allylic alcohols for palladium-catalyzed coupling reactions

We report direct activation of allylic alcohols using a hydrogen-bond-assisted palladium catalyst and use this for alkylation and amination reactions. The novel catalyst comprises a palladium complex based on a functionalized monodentate phosphoramidite ligand in combination with urea additives and affords linear alkylated and aminated allylic products selectively. Detailed kinetic analysis show that oxidative addition of the allyl alcohol is the rate-determining step, which is facilitated by hydrogen bonds between the alcohol, the ligand functional group, and the additional urea additive. Hydrogen Bond Rule(s): Direct activation of allylic alcohols and subsequent alkylation and amination reactions are reported. The new catalyst is based on functionalized palladium and phosphoramidite ligands to allow hydrogen bond-assisted activation. Kinetic data are in line with this mechanism as the oxidative addition is the rate-determining step.

Simple and convenient approach for synthesis of tetrahydroquinoline derivatives and studies on aza-Cope rearrangement

A simple and novel synthesis of 1,2,3,4-tetrahydroquinoline derivatives by polyphosphoric acid-assisted reaction of N-aryl allyl anilines prepared from anilines has been reported. The generality and scope of the approach has been demonstrated by extending it to the synthesis of 1,2,5,6-tetrahydro-4H- pyrrolo[3,2,1-ij]quinoline (lilolidine) and 2,3,6,7-tetrahydro-1H,5H-pyrido[3,2, 1-ij]quinoline (julolidine). Further, Lewis acid- mediated aza-Cope rearrangement of various N-aryl allyl anilines has been demonstrated.

Pd(OAc)2/dppf as an efficient and highly active catalyst for the allylation of amines, alcohols and carboxylic acids with 1-phenyl-1-propyne

Pd(OAc)2/1,1′-bis(diphenylphosphino)ferrocene as an efficient, highly active catalyst for the allylation of amines, alcohols and carboxylic acids with 1-phenyl-1-propyne has been developed. The effect of various reaction parameters, such as ligand, time, solvent, temperature, metal: ligand ratio and catalyst concentration on yields of the product were investigated. The optimized procedure works well under mild operating conditions and permits rapid generation of a library for various allylated products.

Tsuji-Trost allylations with palladium recovery by phosphines/Pd(0)-triolefinic macrocyclic catalysts

The allylation of several nitrogen and oxygen based nucleophiles with ethyl cinnamyl carbonate under mild conditions is described. The processes take place in the absence of added base and in the presence of the precatalytic system Pd(0)-triolefinic macrocycle/1,1′-bis(diphenylphosphino)ferrocene. The macrocyclic ligand plays a key role in the recovery of the metal in the form of the initial macrocyclic complex.

Allylic amination of internal alkynes with aromatic and aliphatic amines using polymer-supported triphenylphosphane-palladium complex as a heterogeneous and recyclable catalyst

A facile and novel protocol for the allylic amination of internal alkynes with amines by using a polymer-supported triphenylphosphane-palladium complex [PS-TPP-Pd] as a highly active heterogeneous reusable catalyst was developed. The catalyst exhibited remarkable activity and is re-usable over five consecutive cycles. The protocol was applicable for a variety of hindered and functionalized aromatic/ aliphatic amines and afforded the desired allylic products in good to excellent yield.

Nucleophilic substitution reactions of alcohols with use of montmorillonite catalysts as solid Bronsted acids

(Chemical Equation Presented) We have developed an environmentally benign synthetic approach to nucleophilic substitution reactions of alcohols that minimizes or eliminates the formation of byproducts, resulting in a highly atom-efficient chemical process. Proton- and metal-exchanged montmorillonites (H- and Mn+-mont) were prepared easily by treating Na +-mont with an aqueous solution of hydrogen chloride or metal salt, respectively. The H-mont possessed outstanding catalytic activity for nucleophilic substitution reactions of a variety of alcohols with anilines, because the unique acidity of the H-mont catalyst effectively prevents the neutralization by the basic anilines. In addition, amides, indoles, 1,3-dicarbonyl compounds, and allylsilane act as nucleophiles for the H-mont-catalyzed substitutions of alcohols, which allowed efficient formation of various C-N and C-C bonds. The solid H-mont was reusable without any appreciable loss in its catalytic activity and selectivity. Especially, an Al3+-mont showed high catalytic activity for the α-benzylation of 1,3-dicarbonyl compounds with primary alcohols due to cooperative catalysis between a protonic acid site and a Lewis acidic Al3+ species in its interlayer spaces.

Gold-catalyzed direct amination of allylic alcohols

An efficient and direct synthesis of allylic amines from allylic alcohols was developed by utilization of gold complexes as catalysts under mild reaction conditions. AuCl3 proved to be a better catalyst than a cationic gold(I) complex of AuCl(PPh3)/AgOTf. Georg Thieme Verlag Stuttgart.

Direct palladium/carboxylic acid-catalyzed allylation of anilines with allylic alcohols in water

The direct activation of C-O bonds in allylic alcohols in water as a suspension medium by palladium complexes has been accelerated by carrying out the reactions in the presence of a carboxylic acid. The palladium-catalyzed allylation of anilines using allylic alcohols directly gave allylic anilines in good yields.

Palladium-catalyzed allylation of acidic and less nucleophilic anilines using allylic alcohols directly

The direct activation of C-O bonds in allylic alcohols by palladium complexes has been accelerated by carrying out the reactions in the presence of titanium(IV) isoproxide and 4 A molecular sieves. The acidic and less nucleophilic anilines such as diphenylamine, phenothiazine, 4-cyanoaniline, and nitroanilines are efficiently allylated under palladium catalysis using allylic alcohols as allylating reagents.

A convenient and efficient route for the allylation of aromatic amines and α-aryl aldehydes with alkynes in the presence of a Pd(0)TPhCOOH combined catalyst system

The allylation of aromatic amines with alkynes proceeded smoothly in the presence of catalytic amounts of Pd(PPh3)4 and benzoic acid. The allylation products were obtained in high yields in a regio- and stereoselective manner. The effect of various groups on the nitrogen atom of anilines was studied. Regardless of the substituent (electron withdrawing or electron donating) on the aromatic ring, the reaction proceeded well. Various functionalities, including -CH3, -OMe, -Cl, -CN, -COOMe, -NO 2 and -COCH3 were tolerated under the reaction conditions. Similarly, the allylation of α-aryl aldehydes proceeded well with the same level of regio- and stereoselectivity as the allylation of aromatic amines. This reaction provides the second example of the transition metal catalyzed direct α-allylation of aldehydes.