3508-79-0

Upstream product

• 107-18-6 allyl alcohol 
• 123-54-6 acetylacetone 
• 106-95-6 allyl bromide 
• 85021-16-5 allyl N-phenyliminobenzoate 
• 591-87-7 Allyl acetate 
• 107-05-1 3-chloroprop-1-ene 
• 3508-78-9 3-allyl-2,4-pentanedione 
• 5666-17-1 N,N-diethylallylamine 
• 17686-63-4 acetone O-<(allyloxy)-carbonyl>oxime 
• 35466-83-2 allyl methyl carbonate 

Downstream Products

• 139591-74-5 1-[1-Acetyl-3-bromomethyl-4-(toluene-4-sulfonylmethyl)-cyclopentyl]-ethanone 
• 132603-75-9 1,1-diacetyl-3-(3-ethoxycarbonyl-3-buten-1-yl)-4-p-toluenesulfonylmethyl-cyclopentane 
• 132603-75-9 1,1-diacetyl-3-(3-ethoxycarbonyl-3-buten-1-yl)-4-p-toluenesulfonylmethyl-cyclopentane 
• 3508-78-9 3-allyl-2,4-pentanedione 
• 57620-44-7 3a-allyl-6-benzoyloxy-3,5,6a-trimethyl-4,5,6,6a-tetrahydro-3aH-pyrrolo[3,2-d]isoxazole 

Relevant academic research and scientific papers

Silica Support-Enhanced Pd-Catalyzed Allylation Using Allylic Alcohols

Although allylation using allylic alcohol is an environmentally-friendly method because of water being the sole byproduct in such reactions, allylic alcohol is one of the most difficult allylating agents in Pd-catalyzed allylation of nucleophiles. In this study, we successfully developed a mesoporous silica-supported Pd complex as an efficient catalyst for the allylation of nucleophiles using allylic alcohols as allylating agents. The allylic alcohol is activated by the silanol group on the support surface, which easily undergoes a π-allylpalladium intermediate formation. The catalytic activity of the supported Pd complex was ca. 9 times higher than that of its homogeneous precursor Pd complex. A highest turnover number of 4500 based on Pd was achieved. Various nucleophiles and allylic alcohol derivatives could be used as substrates. Not only the detailed catalyst structure but also the reaction mechanism including the concerted activation of allylic alcohol by the Pd complex and silanol were investigated by several spectroscopic techniques, such as Pd K-edge XAFS, solid-state NMR, and in-situ FT-IR measurements.

Highly efficient Tsuji-Trost allylation in water catalyzed by Pd-nanoparticles

Palladium nanoparticles stabilized by poly(vinylpyrrolidone) catalyze Tsuji-Trost allylations in water with very high turnover numbers. The di-allylation of methylene active compounds and the allylation of bio-based phenols was performed in high yield. The allylation of lignin showed a high selectivity towards the phenolic OH groups.

Highly selective palladium-benzothiazole carbene-catalyzed allylation of active methylene compounds under neutral conditions

The Pd-benzothiazol-2-ylidene complex I was found to be a chemoselective catalyst for the Tsuji-Trost allylation of active methylene compounds carried out under neutral conditions and using carbonates as allylating agents. The proposed protocol consists in a simplified procedure adopting an in situ prepared catalyst from Pd2dba3 and 3-methylbenzothiazolium salt V as precursors. A comparison of the performance of benzothiazole carbene with phosphanes and an analogous imidazolium carbene ligand is also proposed.

Tsuji-Trost allylation of CH acids in supercritical carbon dioxide: Advantages and problems

The Pd(PPh3)4-catalyzed reaction between α-cyano or β-oxo carboxylates and allyl acetate in supercritical carbon dioxide with the K2CO3-18-crown-6 system as a base affords exhaustive allylation products in high yields, whereas malononitrile and acetylacetone of higher CH acidity form the mixtures of mono- and diallylated derivatives in moderate yields.

Efficient allylation of nucleophiles catalyzed by a bifunctional heterogeneous palladium complex-tertiary amine system

We demonstrate the synergistic catalysis of a silica-supported diaminopalladium complex and a tertiary amine (SiO2/diamine/Pd/ NEt2) as well as synthetic scope of the Tsuji-Trost reaction of 1,3-dicarbonyls, phenols, and carboxylic acids with allyl carbonate and acetates. The synergistic catalysis of SiO2/diamine/Pd/NEt 2 exhibited wide applicability and high activity for the Tsuji-Trost reaction. For example, the reaction of ethyl 3-oxobutanate with allyl methyl carbonate afforded the allylated product in >99% yield at 70 °C for 5 h. The yield of allylated products was 26% for SiO2/diamine/Pd, without immobilization of the tertiary amine group. In the reaction of 1.0 mmol of ethyl 3-oxobutanate using 0.60 μmol of Pd in SiO2/diamine/Pd/NEt 2, the turnover number (TON) of Pd reached up to 1070 within 24 h. Phenols with electron-withdrawing groups, such as nitro and chloro groups, on the para position resulted in high product yields. The SiO2/diamine/ Pd/NEt2 catalyst was reusable at least 4 times without appreciable loss of its activity and selectivity in the reaction of p-chlorophenol. Copyright

First iodine-catalyzed deallylation of reactive allyl methylene esters

C-Allyl cleavage has been developed using the inexpensive and mild reagent iodine in dimethylsulfoxide. A variety of compounds with active methylene groups were C-deallylated using this reagent. This method is efficient and operationally simple in comparison to the methods using transition-metal complexes. Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications to view the free supplemental file.

Ruthenium-Catalyzed One-Pot Double Allylation/Cycloisomerization of 1,3-Dicarbonyl Compounds Leading to exo-Methylenecyclopentanes

The ruthenium-catalyzed one-pot double allylation/cycloisomerization of 1,3-diketones and methyl acetoacetate gave exo-methylenecyclopentanes in moderate to good yields with high isomer selectivity. The double allylation step effectively proceeded in the presence of a RuII precatalyst, [Cp*RuCl(cod)], in 1,2-dichloroethane at 90°C. The subsequent cycloisomerization was carried out upon addition of triethylsilane as a hydride source without purification of a 1,6-diene intermediate. Detailed inspections of the reaction by 1H NMR spectroscopy disclosed that triethylsilyl methyl ether plays an important role for the conversion of a ruthenium(IV) allyl complex formed in the double allylation step into a ruthenium(II) species required for the cycloisomerization.

Palladium-tetraphosphine complex: An efficient catalyst for allylic substitution and Suzuki cross-coupling

A new tetraphosphine, the cis-cis-cis-1,2,3,4-tetrakis (diphenylphosphinomethyl)cyclopentane (Tedicyp) has been synthesized and used in palladium-catalyzed reactions. This tetraphosphine in combination with [Pd(C3H5)Cl]2 affords a very efficient catalyst for coupling reactions. Turnover numbers of 980 000 for allylic amination, 9 800 000 for allylic alkylation and 97 000 000 for Suzuki cross-coupling can be obtained in the presence of this catalyst.

A new tetratertiary phosphine ligand and its use in Pd-catalyzed allylic substitution

A new tetraphosphine, the cis-cis-cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane (Tedicyp) 1 has been synthesized, characterized, and used in Pd-catalyzed allylic substitutions. The Tedicyp was easily prepared in seven steps from the commercially available himic anhydride. The structure of the complex Tedicyp-borane was determined by X-ray analysis. The tetraphosphine in combination with [Pd(η3-C3H5)Cl]2 affords a very efficient catalyst for allylic substitution of several allylic acetates. Under mild conditions, very high turnover numbers and turnover frequencies have been obtained.