7642-42-4

Upstream product

• 673-32-5 1-Phenylprop-1-yne 
• 1600-27-7 mercury(II) diacetate 
• 108-22-5 Isopropenyl acetate 
• 93-55-0 1-phenyl-propan-1-one 
• 108-24-7 acetic anhydride 
• 64-19-7 acetic acid 
• 83808-03-1 1-phenylpropyl acetate 

Relevant academic research and scientific papers

Rh-catalyzed asymmetric hydrogenation of α-aryl-β-alkylvinyl esters with chiral ferrocenylphosphine-phosphoramidite ligand

An enantioselective Rh-catalyzed hydrogenation of E/Z mixtures of trisubstituted vinyl esters has been disclosed. With a combination of [Rh(COD)2]BF4 and a structurally fine-tuning chiral ferrocenylphosphine-phosphoramidite ligand as the catalyst, a variety of E/Z mixtures of α-aryl-β-alkylvinyl esters have been successfully hydrogenated in high yields and with good to high enantioselectivities (up to 96% ee). The presence of a small amount of tBuOH proved to be beneficial to improve the hydrogenation outcome.

Asymmetric Oxidation of Enol Derivatives to α-Alkoxy Carbonyls Using Iminium Salt Catalysts: A Synthetic and Computational Study

We report herein the first examples of asymmetric oxidation of enol ether and ester substrates using iminium salt organocatalysis, affording moderate to excellent enantioselectivities of up to 98% ee for tetralone-derived substrates in the α-hydroxyketone products. A comprehensive density functional theory study was undertaken to interpret the competing diastereoisomeric transition states in this example in order to identify the origins of enantioselectivity. The calculations, performed at the B3LYP/6-31G(D) level of theory, gave good agreement with the experimental results, in terms of the magnitude of the effects under the specified reaction conditions, and in terms of the preferential formation of the (R)-enantiomer. Just one of the 30 characterized transition states dominates the enantioselectivity, which is attributed to the adoption of an orientation relative to stereochemical features of the chiral controlling element that combines a CH interaction between a CH2 group in the substrate and one of the aromatic rings of the biaryl section of the chiral auxiliary with a good alignment of the acetoxy group with the other biaryl ring, and places the smallest substituent on the alkene (a hydrogen atom) in the most sterically hindered position.

Visible light induced C-H monofluoroalkylation to synthesize 1,4-unsaturated compound

We developed a method to synthesize fluorinated 1,4-unsaturated dicarbonyl compounds via photoredox catalyzed radical addition process. Commercially available ethyl bromodifluoroacetate (BrCF2CO2Et) as fluoroalkyl source, the corresponding fluoro-containing dicarbonyl compounds could be obtained in moderate to good yields.

First lipase catalysed resolution of epoxy enol esters

We report the first enzyme-catalysed kinetic resolution of epoxy enol esters. The lipase-promoted hydrolysis of these compounds provided α-hydroxyketones or α-hydroxyaldehydes (arising from the spontaneous rearrangement of the epoxy enols) and the residual esters with moderate to good enantioselectivity (E up to 100).

Homolytic carbostannylation of alkenes and alkynes with tributylstannyl enolates

matrix presented In the presence of AIBN, tributylstannyl enolates derived from aromatic ketones reacted with electron-deficient alkenes and a variety of alkynes to give the corresponding carbostannylated adducts. The reactions with methyl acrylate gave α-tributylstannylmethyl-γ-ketoesters, unlike the known Michael-type reaction of stannyl enolates forming δ-ketoesters. The carbostannylation of alkynes proceeded in an anti addition mode to afford β,γ-unsaturated ketones. The reactivity of stannyl enolates as radical transfer agents could be utilized for radical cyclization of 1,6-enynes.

Thermal and photochemical solvolysis of (E)- and (Z)-2-phenyl-1-propenyl(phenyl)iodonium tetrafluoroborate: Benzenium and primary vinylic cation intermediates

The thermal and photochemical solvolysis of the two stereoisomeric 2-phenyl-1-propenyl(phenyl)-iodonium tetrafluoroborates has been investigated in alcoholic solvents of varying nucleophilicity. The product profiles and rates of product formation in the thermal reaction are all compatible with a mechanism involving cleavage of the vinylic C - I bond assisted by the group in the trans position (methyl or phenyl), always leading to rearranged products. Depending on the nucleophilicity of the solvent, the primarily formed cations may or may not further rearrange to more stable isomers. The less reactive Z compound also yields some unrearranged vinyl ether product in the more nucleophilic solvents via an in-plane SN2 mechanism. The mechanism of the photolysis involves direct, unassisted cleavage of the vinylic, and aromatic, C - I bond in an SN1 mechanism. This produces a primary vinyl cation, which is partially trapped prior to rearrangement in methanol. The unrearranged vinyl ethers are mainly formed with retention of configuration via a λ3-iodonium/solvent complex in an SNi mechanism. Thermal and photochemical solvolyses of iodonium salts are complementary techniques for the generation of different cation intermediates from the same substrate.

STEREOSELECTIVE ALDOL CONDENSATIONS OF ORGANOTIN REAGENTS WITH ALDEHYDES

The reaction of the enolstannanes of cyclohexanone or propiophenone with various aldehydes under kinetic control (-78 deg C) gave predominately the threo aldols, diastereoselectivity as high as 95:5 being achived.At higher temperatures (+45 deg C) predominate erythro selectivity was observed.The enolstannane of propiophenone exists as an equilibrium mixture of O-Sn (probably the E-isomer) and C-Sn derivatives.Reaction at -78 deg C takes place rapidly with the O-Sn enolate, further reaction requiring isomerization of the C-Sn to the O-Sn enolate.The Pd catalyzed condensation of cyanomethyltributyltin with reactive aldehydes, such as nitrobenzaldehydes, took place at ambient temperatures in polar solvents to give high yields of condensation products.No reaction occured with aldehydes such as benzaldehyde.Only low stereoselectivity (10-34percent ee) was observed when (-)DIOP or (-)BPPM were utilized as chiral phosphine ligands.

Regio- and Stereo-selectivity of Acetoxymercuration of Acetylenes

Acetoxymercuration of alkylphenylacetylenes (PhCCR; R = Me, Et, Prn, or Bun) (1) in acetic acid at 20 - 60 deg C proceeds completely in a trans-fashion to afford a regioisomeric mixture of two vinylmercury(II) compounds, Ph(OAc)C=C(HgCl)R (2) and Ph(HgCl)C=C(OAc)R (3), the extent of attack of Hg at the carbon α to alkyl group to form (2) being increased upon increasing the carbonyl chain length of the alkyl group .A bridged mercurinium ion intermediate in which phenyl and alkyl groups are bent toward the attacking side of acetate anion is proposed for explaining a marked dependence of the isomer ratio (2):(3) on the kind of alkyl groups.Similar treatment of diphenylacetylene at 20 - 95 deg C gives only the cis-adduct as reported previously, while that of diethyl-acetylene affords the trans-adduct and a mixture of trans- and cis-adduct at 20 deg C and at 65 deg C, respectively.The NaBH4 reduction of (2, R = Me) in neutral condition produces a mixture of (Z)- and (E)-1-acetoxy-1-phenylpropene (ca. 3-5:1) in contrast to the reduction of thallium analogue of (2) which gives only the Z-isomer.