80006-87-7

Upstream product

• 4392-24-9 3-bromo-1-phenyl-1-propenyl bromide 
• 75-98-9 Trimethylacetic acid 
• 3282-30-2 pivaloyl chloride 
• 4407-36-7 (2E)-3-phenyl-2-propen-1-ol 
• 300-57-2 allylbenzene 
• 1538-75-6 2,2-dimethylpropanoic anhydride 
• 106625-69-8 ethyl (E)-3-phenyl-2-propenyl carbonate 
• 1184-88-9 sodium pivalate 
• 673-32-5 1-Phenylprop-1-yne 
• 18997-19-8 Chloromethyl pivalate 
• 1779-49-3 Methyltriphenylphosphonium bromide 
• 100-52-7 benzaldehyde 

Downstream Products

• 20068-10-4 (E)-4-phenyl-3-butenenitrile 
• 1401467-22-8 (R)-methyl 2,2-dimethyl-3-phenylpent-4-enoate 
• 1076-66-0 3-phenyl-1,5-hexadiene 
• 56644-04-3 (E)-1-phenyl-1,5-hexadiene 
• 108400-97-1 ethyl (4E)-2-acetyl-5-phenylpent-4-enoate 
• 55666-17-6 (1E)-1,4-pentadienylbenzene 
• 16215-11-5 trans-cinnamyl p-tolyl sulfone 

Relevant academic research and scientific papers

Enantioselective synthesis of acyclic allylic esters catalyzed by a palladium/BINAP(S) system

The synthesis of chiral nonracemic acyclic allylic pivalates via the Pd-catalyzed allylic substitution of racemic allylic carbonates is presented. Good to excellent enantioselectivities (up to 90%) were observed in several cases. An extraordinarily high preference for the production of the branched regioisomeric product is seen when starting from 3-buten-2-yl and crotyl substrates. A significant kinetic resolution (krel = 38) of the 1,3-dimethylallyl substrate was also observed, leading to the production of esters of both enantiomers of an allylic alcohol with a single enantiomer of catalyst.

Palladium-Catalyzed Allylation of Polyfluoroarenes with Allylic Pivalates

An efficient 1,5-cyclooctadiene-PdCl 2 /dicyclohexyl(2′,4′,6′-triisopropylbiphenyl-2-yl)phosphine (XPhos) catalytic system was developed for C-H allylation of polyfluoroarenes with allylic pivalates. The reactions showed excellent functional-group tolerance, good yields, and high regioselectivities. Mechanistic investigations supported a (π-allyl)palladium complex pathway through a directed oxidative addition of the allylic pivalate to palladium, followed by sequential nucleophilic attack by the polyfluorobenzene and reductive elimination. In a gram-scale reaction, a palladium loading of 0.5 mol% was enough to afford the required product in good yield.

Nickel-Catalyzed Cyanation of Benzylic and Allylic Pivalate Esters

A nickel-catalyzed cyanation reaction of benzylic and allylic pivalate esters is reported using an air-stable Ni(II) precatalyst and substoichiometric quantities of Zn(CN)2. Alkene additives were found to inhibit catalysis, suggesting that avoiding β-hydride elimination side reactions is essential for productive catalysis. An enantioenriched allylic ester undergoes enantiospecific cross-coupling to produce an enantioenriched allylic nitrile. This method was applied to an efficient synthesis of (±)-naproxen from commercially available starting materials.

Direct asymmetric α-allylation of α-branched aldehydes by two catalytic systems with an achiral Pd complex and a chiral primary α-amino acid

Direct α-allylation of α-branched aldehydes was successfully carried out with a readily available allyl ester by combined use of two catalytic systems: Tsuji-Trost allylation reaction with an achiral palladium complex and enamine catalysis with a chiral primary α-amino acid. A quaternary carbon stereogenic center was constructed stereoselectively to give various 2,2-disubstituted pent-4-enals in good yields with high enantioselectivity.

Disubstituted Z-allylic esters by Wittig-Schlosser reaction using methylenetriphenylphosphorane

β-Lithiooxyphosphonium ylides, generated in situ from aldehydes and methylenetriphenylphosphorane, react with halomethyl esters to form disubstituted allylic esters in good yields and with high Z-selectivity.

Palladium-catalyzed allylic acyloxylation of terminal alkenes in the presence of a base

"Chemical Equation Presentation" The efficiency and the selectivity of the Pd-catalyzed oxidation, in carboxylic acids, of terminal alkenes are strongly improved in the presence of a base. The methodology is particularly well adapted for the oxidation of homoallylic alcohols, for which the resulting acyloxylated products are obtained selectively as E-isomers in fair to good yields. 2010 American Chemical Society.

Magnesium bistrifluoromethanesulfonimide as a new and efficient acylation catalyst

Magnesium bistrifluoromethanesulfonimide catalyzed the acetylation of phenols, alcohols, and thiols under solvent-free conditions at room temperature and in short times. Electron-deficient and sterically hindered phenols provided excellent yields. The catalyst was found to be general for acylation with other anhydrides, such as propionic, isobutyric, pivalic, chloroacetic, and benzoic anhydrides. The rate of acylation was influenced by the electronic and steric factors associated with the anhydride. The reaction with less electrophilic anhydrides (e.g., chloroacetic and benzoic anhydrides) required higher temperature (～80 °C). Chemoselective acetylation, pivalation, and benzoylation took place with acid-sensitive alcohols without any competitive dehydration/rearrangement.

Nucleophilic acyl substitutions of anhydrides with protic nucleophiles catalyzed by amphoteric, oxomolybdenum species

(Chemical Equation Presented) Among six different group VIb oxometallic species examined, dioxomolybdenum dichloride and oxomolybdenum tetrachloride were the most efficient catalysts to facilitate nucleophilic acyl substitution (NAS) of anhydrides with a myriad array of alcohols, amines, and thiols in high yields and high chemoselectivity. In contrast to the well-recognized redox chemical behaviors associated with oxomolybdenum(VI) species, the catalytic NAS was unprecedented and tolerates virtually all kinds of functional groups. By using benzoic anhydride as a mediator for in situ generation of an incipient mixed anhydride-MoO2Cl2 adduct with a given functional alkanoic acid, one can achieve oleate, dipeptide, diphenylmethyl, N-Fmoc-α-amino, pyruvic, and tert-butylthio ester, N-tert-butylamide, and trityl methacrylate syntheses with appropriate protic nucleophiles. The amphoteric character of the Mo=O unit in oxomolybdenum chlorides was found to be responsible for the catalytic NAS profile as supported by a control NAS reaction of using an authentic adduct-MoOCl2(O2-CBu t)2 between pivalic anhydride and MoO2Cl 2 as the catalyst.

Palladium-catalyzed coupling of alkynes with alcohols and carboxylic acids

The palladium-catalyzed coupling of alkynes with alcohols and carboxylic acids to give allylic ethers and esters has been achieved. With phenols, these conditions furnish the C-alkylation products.