Hydroarylation Of Norbornene Research Articles

Heterogeneously-catalyzed competitive hydroarylation/hydromination of norbornene with aniline in the presence of Aquivion® ionomer

The hydroarylation of alkenes with aniline is a reaction of high interest, in particular for the manufacture of polyurethanes. This reaction has been mostly investigated in the presence of homogeneous catalysts. So far, heterogeneous catalysts have been scarcely reported for this reaction, mainly due to their inherent low activity and deactivation during the course of the reaction. Here we report the catalytic performance of Aquivion® ionomer, a perfluorinated solid acid polymer, in the hydroarylation of norbornene with aniline. We show that Aquivion® ionomer was robust and can be recycled for at least 6 runs without any decrease of its catalytic performances. Our results also highlight that Aquivion® ionomer improves the propensity of aniline to react through its aromatic ring, thus yielding a higher proportion of hydroarylation products as compared to other tested homogeneous and heterogeneous catalysts.

An unusual endo-selective C-H hydroarylationof norbornene by the Rh(I)-catalyzed reactionof benzamides

Hydroarylation is an environmentally attractive strategy which incorporates all of the atoms contained in the substrates into the desired products. Almost all the hydroarylations of norbornene reported to date involve an exo-selective reaction. Here we show the endo-selective hydroarylation of norbornene in the Rh(I)-catalyzed reaction of aromatic amides. The addition of sterically bulky carboxylic acids enhances the endo-selectivity of the reaction. The results of deuterium-labeling experiments show that both the ortho-carbon and the ortho-hydrogen atoms of aromatic amides were attached to the same carbon atom of the norbornane skeleton in the hydroarylation product. These results clearly suggest that hydrometalation or carbometalation, which are commonly accepted mechanisms for the catalytic hydroarylation of C–H bonds, are not involved as the key step in the present reaction, and suggest that the reaction involves a rhodium carbene complex generated from norbornene as the key intermediate.

Catalytic properties of chiral terpenoid CN-palladacycle in the C—C bond forming reactions

Chiral camphor-derived CN-palladacycle exhibits high catalytic activity in the Suzuki crosscouplings and hydroarylation of norbornene under mild conditions.

Synthesis and catalytic activity of a complex of 1,1´-bis-isoquinoline N,N´-dioxide with PdCl2

A novel complex of 1,1´-bis-isoquinoline N,N´-dioxide with PdCl2 was synthesized. This complex efficiently catalyzes the Suzuki cross-couplings and hydroarylation of norbornene.

Cyclopalladated complex of 1-ferrocenylisoquinoline

A new dimeric cyclopalladated ferrocenyl complex di-µ -chloro-bis[2-(1-isoquinolinyl)ferrocenyl](C,N)dipalladium was obtained and characterized. Its catalytic properties in the Heck and Suzuki reactions (including a solid-phase version), as well as in hydroarylation of norbornene, were studied.

Palladium nanocarbon catalysts (Pd/CNT) as potential enantioselective heterogeneous systems. The behavior in the hydrogenation and hydroarylation of unsaturated substrates

Hydroxy-CNT were modified with optically active α-amino acids. The resulting chiral derivatives were directly palladated with Pd2dba3 and used to catalyze the hydrogenation of α-acetamidostyrene and α-phenylcinnamic acid as well as the hydroarylation of norbornene with iodoarenes. All the catalytic reactions afforded products containing a new chiral carbon center in high yields, though as racemates. Apparently, asymmetric induction is precluded because the palladium sites on the CNT surface are spatially apart from the chiral carbon centers in amino acid groups.

Synthesis, structure, and catalytic activity of complexes of 1,1′-bisisoquinoline with PdCl2 and NiCl2

New complexes of 1,1′-bisisoquinoline with PdCl2 and NiCl2 were synthesized. The structures of the complexes were established by X-ray diffraction. The Pdii complex acts as a catalyst for the Suzuki and Heck reactions and the hydroarylation of norbornene. As exemplified by the Suzuki reaction, the Niii complex can also be used as a catalyst.

ChemInform Abstract: Norbornene Hydroarylation Catalyzed by Ferrocene Palladacycle Complexes.

Two ferrocene derivatives containing palladacycles with bidentate (C,N) and tridentate (C,N,N) ligands were successfully used as catalysts for the hydroarylation of norbornene.

Norbornene hydroarylation catalyzed by ferrocene palladacycle complexes

Two ferrocene derivatives containing palladacycles with bidentate (C,N) and tridentate (C,N,N) ligands were successfully used as catalysts for the hydroarylation of norbornene.

ChemInform Abstract: Highly Efficient Phosphapalladacyclic Catalysts for the Hydroarylation of Norbornene.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Palladium — Catalyzed Reactions, 1 Palladium‐Catalyzed Enantioselective Hydrophenylation and Hydrohetarylation of Bicyclo[2.2.1]Hept‐2‐ene: Influence of the Chiral Ligand, the Leaving Group, and the Solvent

AbstractThe use of optically active biaryl bisphosphanes 10–12, a diphenylphosphanylphenyloxazoline 8, and a (β‐N‐sulfonyl‐aminomethyl)bisdiphenylphosphane 7 as ligands in the Pd‐catalyzed Heck‐type hydroarylation of norbornene (1) with phenyl 2 and various hetaryl derivaties 3–5 leads exclusively to the formation of exo‐2(het)arylnorbornanes 6 with asymmetric inductions of up to 86.4% ee. In addition to an investigation into the effects of different chiral ligands, a systematic study has been made of the influence of various (het)aryl compounds, leaving groups, and solvents on the chemical and optical yields of this reductive arylation.

ChemInform Abstract: Asymmetric Reactions Catalyzed by Chiral Metal Complexes. Part 59. Asymmetric Heck‐Type Hydroarylation of Norbornene (I) with Phenyl Triflate (II) Catalyzed by Palladium Complexes of Chiral (β‐N‐ Sulfonylaminoalkyl)phopshines.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.