72335-26-3

Upstream product

• 32002-24-7 ethyl 3,3-diethoxyacrylate 
• 4407-36-7 (2E)-3-phenyl-2-propen-1-ol 
• 87802-71-9 (E)-methyl cinnamyl carbonate 
• 105-53-3 diethyl malonate 
• 106625-70-1 ethyl (1-phenylallyl) carbonate 
• 36195-56-9 (E)-but-2-en-1-yl phenyl sulfide 
• 5848-60-2 (E)-1-phenyl-3-(phenylthio)propene 
• 16215-11-5 trans-cinnamyl p-tolyl sulfone 
• 69562-10-3 1-phenyl-3-phenylseleno-1-propene 
• 85217-69-2 cinnamyl methyl carbonate 
• 4393-06-0 1-Phenyl-2-propen-1-ol 
• 21040-45-9 Cinnamyl acetate 
• 685-87-0 Diethyl 2-bromomalonate 
• 77134-01-1 (Z)-cinnamyl acetate 

Relevant academic research and scientific papers

Microwave mediated palladium-catalysed reactions on potassium fluoride/alumina without use of solvent

Potassium fluoride on alumina was used in palladium-catalysed reactions (Suzuki, Heck, Stille, Trost-Tsuji) without solvent under mono-mode microwave irradiation. Some reactions took place in air. The organotin residue in the Stille reaction remained on the solid support.

Iridium/ N-Heterocyclic Carbene Complex-Catalyzed Intermolecular Allylic Alkylation Reaction

N-Heterocyclic carbenes (NHCs) were found to be suitable ligands in Ir-catalyzed intermolecular allylic alkylation reaction. In the presence of a catalyst derived from [Ir(dncot)Cl]2 (dncot = dinaphthocyclooctatetraene) and triazolium salt L7,

Iridium complex-catalyzed allylic alkylation of allylic esters and allylic alcohols: Unique regio- and stereoselectivity

An iridium complex was found to be an efficient catalyst for allylic alkylation of allylic esters with a stabilized carbon nucleophile. Highly regioselective alkylation at the substituted allylic terminus was achieved. The catalytic activity and regioselectivity were affected by the ligand used. The reaction of (E)-2-alkenyl acetates or 1-substituted 2-propeny acetates with dialkyl sodiomalonate in the presence of a catalytic amount of [Ir(COD)Cl]2/P(OPh)3 (P/Ir = 1-2) gave a product alkylated at the substituted allylic terminus in 95-99% selectivity. Construction of a quaternary carbon center is possible by this methodology. The reaction of 1,1-dialkyl-2-propenyl acetates gave a product alkylated at the disubstituted allylic terminus exclusively. (E)-2-Alken-1-ol could be successfully used as a substrate. The products alkylated at the substituted allylic terminus were obtained in 93-99% selectivity. A 31P NMR study of the reaction of [Ir(COD)Cl]2 with P(OPh)3 revealed that a catalytically active species is a monophosphite species. The π-acceptor property of P(OPh)3 promotes a carbonium ion character at the substituted allylic terminus and directs the nucleophilic attack to this position. The stereochemistry of the allyl system affected the regioselectivity. In contrast to the reaction of (E)-2-alkenyl acetates, the reaction of (Z)-2-alkenyl acetates gave a product alkylated at the unsubstituted allylic terminus predominantly. This shows that the regioselectivity of the alkylation of the syn π-allyl iridium intermediate is different from that of the anti π-allyl iridium intermediate. (Z)- Selective allylic alkylation of (Z)-2-alkenyl esters is also possible by iridium catalysis.

Highly selective allylic alkylation with a carbon nucleophile at the more substituted allylic terminus catalyzed by an iridium complex: An efficient method for constructing quaternary carbon centers

The selective construction of quaternary carbon centers, which are frequently found in natural products, is essential to many syntheses. A new method relying on the iridium complex [Ir(cod)Cl]2 as the catalyst can be used for the allylic alkylation of acyclic compounds 1. The products are obtained in yields between 70 and 85% and with a selectivity of 100%, cod = cyclooctadiene.

Ruthenium complex-catalyzed allylic alkylation of carbonucleophiles with allylic carbonates

Allylic carbonates except for allyl methyl carbonate reacted with carbonucleophiles such as ethyl acetoacetate in the presence of a catalytic amount of Ru(cod)(cot) in N-methylpiperidine at 80 deg C to give the corresponding monoallylated carbonucleophiles in high yields with high regioselectivity.The regioselectivity was quite different from that in the palladium-catalyzed reactions.The allylation of carbonucleophiles using allyl methyl carbonate selectively gave the diallylated carbonucleophiles in high yields.

On the Regio- and Stereoselectivity of Bu4N-Catalyzed Allylic Alkylation

Bu4N has been found to catalyze the alkylation of allylic carbonate with malonate anion.The reaction proceeds with good regioselectivity, the nucleophile attacking predominantly at the carbon where the leaving group was attached.Retention of configuration of the double bond during the course of reaction was observed.Alkylation of methyl (Z)-5-carbomethoxy-1-cyclohexen-3-yl carbonate with sodium salt of dimethyl malonate yielded dimethyl ((Z)-5-carbomethoxy-1-cyclohexen-3-yl)malonate in a highly stereoselective fashion, and a net retention of configuration at the center undergoing substitution is thus established.On the basis of regio- and stereochemical results, a reaction pathway involving an ?-allyliron complex has been suggested.

SIGMATROPIC REARRANGEMENT OF ALLYLIC ALCOHOLS WITH ETHYL β,β-DIETHOXYACRYLATE: REGIOSPECIFIC SYNTHESIS OF SUBSTITUTED ALLYLMALONATES.

Sigmatropic rearrangement of allylic alcohols with ethyl β,β-diethoxyacrylate provides a convenient method for the regiospecific synthesis of substituted allylmalonates 3.

PALLADIUM-CATALYZED REACTION OF ALLYLIC AMMONIUM BROMIDES WITH NUCLEOPHILES

The reactions of allylic triethylammonium bromides and dimethylsulfonium bromide with carbon nucleophiles were catalyzed by tetrakis(triphenylphosphine)palladium to afford olefinic esters and ketones.