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Relevant academic research and scientific papers

Palladium-Catalyzed Synthesis of β,β-Diaryl α,β-Unsaturated Ketones

We herein describe a versatile palladium-catalyzed synthesis of β,β-diaryl α,β-unsaturated ketones. A broad range of aryl halides react with β-arylbutanones to afford biologically useful, symmetrical and unsymmetrical ketones. The use of 4,5-diazafluoren-9-one and oxygen makes this one-pot reaction more applicable. A plausible mechanism involving palladium-catalyzed oxidative Heck-type cross-coupling is also proposed.

Importance of the Reducing Agent in Direct Reductive Heck Reactions

The role of the reductant in the palladium N-heterocyclic carbene (NHC) catalyzed reductive Heck reaction and its effect on the mechanism of the reaction is reported. For the first time in this type of transformation, the palladium-NHC-catalyzed reductive

Silver sequestration of halides for the activation of Pd(OAc)2 catalyzed Mizoroki-Heck reaction of 1,1 and 1,2 - Disubstituted alkenes

A ligand free catalytic system consisting of Pd(OAc)2 (cat) and stoichiometric quantities of silver salts, AgOAc or AgBF4, exhibit high efficiency in the Mizoroki-Heck arylation, transforming aryl iodides and 1,1 as well as 1,2 disubstituted alkenes into 1,1,2 – trisubstituted aryl alkenes in excellent yields in very short reaction times.

Palladium(II) Acetate Catalyzed Reductive Heck Reaction of Enones; A Practical Approach

A surprisingly practical Pd(OAc)2 or Pd(TFA)2-catalyzed reductive Heck reaction between aryl iodides and α,β-unsaturated ketones is described using N,N-diisopropylethylamine (DIPEA, Hünigs base) as the reductant. In general, 1 mol % of Pd(OAc)2 is sufficient to afford good yields using electron-rich or halogen-substituted aryl iodides. Electron-deficient aryl iodides preferentially give homocoupling. Enones containing aryl or bulky substituents on the β-carbon react smoothly, producing mainly reductive Heck product, whereas enones with alkyl substituents on the β-carbon afford a mixture of reductive Heck and Heck product. Deuterium labeling experiments show that the reaction is a bona fide reductive Heck reaction and exclude a Heck reaction-conjugate reduction cascade. Deeply DIPEA about... A palladium-catalyzed reductive Heck reaction of aryl iodides to α,β-unsaturated ketones is described using N,N diisopropylethylamine (DIPEA, Hünigs base) as the reductant. A deuterium labeling study shows that the reaction is a bona fide reductive Heck reaction and excludes a Heck reaction-conjugate reduction cascade.

Pd-NHC catalyzed conjugate addition versus the mizoroki-heck reaction

Ace of base: A catalytic system is presented that, solely by choice of the base, selectively switches between conjugate addition and the Mizoroki-Heck reaction of aryl halides with Michael acceptors (see scheme; R, R′=alkyl, aryl). For conjugate addition reactions, this avoids the preparation and use of organometallics.

Tetraphosphine/palladium-catalyzed Heck reactions of aryl halides with disubstituted alkenes

cis,cis,cis-1,2,3,4-Tetrakis(diphenylphosphinomethyl)cyclopentane/ [PdCl(C3H5)]2 efficiently catalyses the Heck reaction of disubstituted alkenes such as methyl crotonate, ethyl cinnamate, methyl methacrylate or α-methylstyrene with a variety of aryl halides. In the presence of 1,2-disubstituted alkenes the stereoselectivities of the reactions strongly depend on the substituents of the alkenes. Selectivities up to 97% in favor of E-isomers can be obtained for the addition to methyl crotonate. With the 1,1-disubstituted alkenes methyl methacrylate or α-methylstyrene mixtures of products are obtained.

Toward waste-free production of heck products with a catalytic palladium system under oxygen

A 100% carbon-efficient, halide- and solvent-free alternative for the synthesis of Heck-type products is the direct oxidative coupling of arenes with olefins, catalyzed by Pd(OAc)2 under oxygen (see scheme). The reactions can be performed under mild conditions, and water is the only by-product. (TON = turnover number, TOF = turnover frequency.).

The utilization of supercritical carbon dioxide in the palladium- catalyzed hydroarylation of β-substituted-α,β-enones

The utilization of supercritical carbon dioxide (scCO2) has a beneficial effect on the palladium-catalyzed reaction of acyclic β- substituted-α,β-enones with aryl iodides and hydroarylation (formal conjugate addition) products were isolated in good to high yields. The hydroarylation to vinylic substitution ratio is usually high.

CONJUGATE ADDITION VS. VINYLIC SUBSTITUTION IN PALLADIUM-CATALYSED REACTION OF ARYL HALIDES WITH β-SUBSTITUTED-α,β-ENONES AND -ENALS

The reaction of β-substituted-α,β-enones and -enals with aryl halides in the presence of a palladium catalyst has been investigated.The outcome of the reaction was found to be greatly dependent on the nature of the added base.Tertiary amines tend to favour the formation of conjugate addition-type products while sodium bicarbonate or sodium acetate that of vinylic substitution products.Usually, the use of sodium acetate produced results comparable or better than those obtained with sodium bicarbonate.Furthermore, in the reaction of aryl halides containing strongly electron-withdrawing groups, sodium acetate afforded a dramatic increase in the yield of vinylic substitution products.