Arylzinc Compounds Research Articles

ChemInform Abstract: The Drastic Effect of Cobalt and Chromium Catalysts in the Borylation of Arylzinc Reagents.

AbstractA drastic additive effect for increasing the reactivity of arylzinc reagents, enabling the borylation of unreactive arylzinc compounds to afford various arylboronic esters is reported.

ChemInform Abstract: Nickel/Bis(oxazoline)‐Catalyzed Asymmetric Negishi Arylations of Racemic Secondary Benzylic Electrophiles to Generate Enantioenriched 1,1‐Diarylalkanes.

AbstractNegishi cross‐coupling reaction of racemic benzylic secondary alcohols with arylzinc compounds affords synthetically valuable enantioenriched 1,1‐diarylalkanes in high yields and enantioselectivities.

The electrochemical reduction of 1-bromo-4-nitrobenzene at zinc electrodes in a room-temperature ionic liquid: a facile route for the formation of arylzinc compounds

The electrochemical reduction of 1-bromo-4-nitrobenzene (p-BrC6H4NO2) at zinc microelectrodes in the [C4mPyrr][NTf2] ionic liquid was investigated via cyclic voltammetry. The reduction was found to occur via an EC type mechanism, where p-BrC6H4NO2 is first reduced by one electron, quasi-reversibly, to yield the corresponding radical anion. The radical anions then react with the Zn electrode to form arylzinc products. Introduction of carbon dioxide into the system led to reaction with the arylzinc species, fingerprinting the formation of the latter. This method thus demonstrates a proof-of-concept of the formation of functionalised arylzinc species.

ChemInform Abstract: Facially Selective Cu‐Catalyzed Carbozincation of Cyclopropenes Using Arylzinc Reagents Formed by Sequential I/Mg/Zn Exchange.

AbstractIn the presence of CuCN, various functionalized arylzinc compounds generated in situ undergo convenient and stereoselective coupling with the cyclopropene (II) to afford cis‐substituted derivatives.

ChemInform Abstract: Carbon Dioxide as a Carbon Source in Organic Transformation: Carbon—Carbon Bond Forming Reactions by Transition‐Metal Catalysts

AbstractReview: 23 refs.

Carbon dioxide as a carbon source in organic transformation: carbon–carbon bond forming reactions by transition-metal catalysts

Recent carbon-carbon bond forming reactions of carbon dioxide with alkenes, alkynes, dienes, aryl zinc compounds, aryl boronic esters, aryl halides, and arenes having acidic C-H bonds are reviewed in which transition-metal catalysts play an important role.

ChemInform Abstract: Palladium‐Catalyzed Coupling Reactions of Tetrafluoroethylene with Arylzinc Compounds.

AbstractThe method allows a new and selective access to various trifluorostyrene derivatives like (III).

ChemInform Abstract: Rh‐Catalyzed Carbonylation of Arylzinc Compounds Yielding Symmetrical Diaryl Ketones by the Assistance of Oxidizing Agents.

AbstractIt provides a highly efficient method to prepare symmetrical diaryl ketones.

Pd-Catalyzed Coupling of Tetrafluoroethylene with Arylzinc Compounds

Pd-Catalyzed Coupling of Tetrafluoroethylene with Arylzinc Compounds

Palladium-Catalyzed Coupling Reactions of Tetrafluoroethylene with Arylzinc Compounds

Organofluorine compounds are widely used in all aspects of the chemical industry. Although tetrafluoroethylene (TFE) is an example of an economical bulk organofluorine feedstock, the use of TFE is mostly limited to the production of poly(tetrafluoroethylene) and copolymers with other alkenes. Furthermore, no catalytic transformation of TFE that involves carbon-fluorine bond activation has been reported to date. We herein report the first example of a palladium-catalyzed coupling reaction of TFE with arylzinc reagents in the presence of lithium iodide, giving α,β,β-trifluorostyrene derivatives in excellent yields.

Rh-Catalyzed Carbonylation of Arylzinc Compounds Yielding Symmetrical Diaryl Ketones by the Assistance of Oxidizing Agents

Carbonylative homocoupling of arylzinc compounds 1 using 1 atm of CO and 1,2-dibromoethane as an oxidant was achieved in the presence of Rh-dppf catalyst, affording symmetrical diaryl ketones in good yields. Under similar conditions, Pd or Ni catalysts induced oxidative homocoupling of 1 to yield biaryls instead. The beneficial catalysis by Rh in the carbonylation was presumed to stem from the facility by which the migration of the aryl ligand to CO at the Rh(3+) intermediate occurred.

ChemInform Abstract: Nucleophilic Additions of Arylzinc Compounds to Aldehydes Mediated by CrCl3: Efficient and Facile Synthesis of Functionalized Benzhydrols, 1(3H)-Isobenzofuranones, Benzyl Alcohols, or Diaryl Ketones.

In the presence of a stoichiometric amount of CrCl(3) and trimethylchlorosilane (TMSCl), nucleophilic addition of arylzinc compounds 1c-h to arylaldehydes 2a,b,g smoothly proceeded at room temperature to yield corresponding benzhydrols 4a-f in good yields. From arylzinc compounds 1a,b, 3-aryl-1(3H)-isobenzofuranones 3a-f were given by the CrCl(3)-mediated reaction with arylaldehydes 2a-f. Diaryl ketones 5a-e were obtained in good yields by the addition of excess amount of benzaldehyde as an oxidant to the resulting solution after the CrCl(3)-mediated reaction between arylzinc compounds 1c-g and arylaldehydes 2b,g was completed. In the nucleophilic additions of arylzinc compounds 1a,d,f to alkyladehydes 6b-f, the treatment of arylzinc compounds with CrCl(3) was required prior to the addition of the aldehydes in order to prevent the fast protodezincation of arylzinc compounds by the enolizable aldehydes. In these CrCl(3)-mediated nucleophilic additions of arylzinc compounds to aldehydes, arylchromium(III) species are probably reactive intermediates.

Negishi Alkyl−Aryl Cross-Coupling Catalyzed by Rh: Efficiency of Novel Tripodal 3-Diphenylphosphino-2-(diphenylphosphino)methyl-2-methylpropyl Acetate Ligand

3-Diphenylphosphino-2-(diphenylphoshino)methyl-2-methylpropyl acetate acted as an efficient ligand for a Rh catalyst, achieving cross-coupling between arylzinc compounds bearing electron-withdrawing groups and alkyl electrophiles. The beneficial effect of the tripodal ligand and such aryl nucleophiles was discussed with regard to the specificity of the Rh catalysis.

Carboxylation of Organozinc Reagents Using CO2 in DMF

This is the first report on the transition-metal-free carboxylation of organozinc compounds. Functionalized alkyl-, alkenyl-, benzylic, and arylzinc compounds prepared by a variety of methods can be involved in this reaction affording good yields of the corresponding acids. This is a simple and useful method for the preparation of functionalized carboxylic acids.

Efficient Cross-Coupling of Aryl Chlorides with Arylzinc Reagents Catalyzed by Amido Pincer Complexes of Nickel

The nickel-catalyzed Negishi cross-coupling reaction of aryl chlorides with arylzinc compounds was investigated. The nickel complexes with the amido pincer type of ligands exhibited high catalytic activity and good functional group tolerance.

Novel Rh Catalysis in Cross‐Coupling Between Alkyl Halides and Arylzinc Compounds Possessing ortho‐COX (X: OR, NMe2, or Ph) Groups.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

Negishi Cross-Coupling of Sulfonyl Chlorides

This is an interesting new example of a transition-metal-catalyzed C-C bond-forming reaction. The coupling proceeds smoothly between aryl sulfonyl chlorides and arylzinc compounds, and to some extent also with alkenyl and allylzinc species. The reaction is practical and uses a commercially available catalyst. It presents a significant interest from the methodological point of view, since it proceeds via an unusual palladium insertion into the S-Cl bond of a sulfonyl chloride, and might lead to a new general novel synthetically useful method of C-C bond formation.

Rh-Catalyzed Coupling of Alkyl Halides with o-Substituted Arylzinc Compounds

Rh-Catalyzed Coupling of Alkyl Halides with <i>o</i>-Substituted Arylzinc Compounds

2,2′‐Bipyridine: An Efficient Ligand in the Cobalt‐Catalyzed Synthesis of Organozinc Reagents from Aryl Chlorides and Sulfonates.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

Negishi coupling strategy of a repetitive two-step method for oligoarene synthesis

A novel repetitive two-step method for oligoarene synthesis, based on Negishi cross-coupling of zinciophenoxides or zinciopyridinoxides with aryl triflates and subsequent triflation of the hydroxy group, was developed. Reaction conditions were optimized for the preparation of the arylzinc compounds and the palladium-catalyzed cross-coupling step.