Oxidative Aryl Coupling Research Articles

Metal–Organic Framework-Derived p-Type Cu3P/Hexagonal Boron Nitride Nanostructures for Photocatalytic Oxidative Coupling of Aryl Halides to Biphenyl Derivatives

Metal–Organic Framework-Derived p-Type Cu₃P/Hexagonal Boron Nitride Nanostructures for Photocatalytic Oxidative Coupling of Aryl Halides to Biphenyl Derivatives

Perfluorocyclopentadienyl Radical Derivative as an Organocatalyst for Oxidative Coupling of Aryl- and Thienylmagnesium Compounds under Atmospheric Oxygen.

The oxidative homocoupling reaction of Grignard reagents in the presence of atmospheric oxygen molecules proceeded in the presence of a heptafluorotolyl-substituted perfluorocyclopentadienyl radical. The turnover number (TON) was over 30 for the coupling reactions of PhMgBr to give biphenyl. The organocatalyst could couple thienylmagnesium compounds to give bithiophene derivatives in up to 94% yield. Furthermore, a gram-scale synthesis of 6,6'-dimethoxybiphenyl-2,2'-diyl-bis(phosphonic acid diethyl ester) was demonstrated. Stabilization of the phenyl radical for the inhibition of the side reaction was also considered using DFT calculations.

Palladium-catalyzed oxidative coupling of arylboronic acid with isocyanide to form aromatic carboxylic acids.

A valuable palladium-catalyzed oxidative coupling of aryl- and alkenyl borides with isocyanide for the synthesis of corresponding carboxylic acids has been developed. With wide substrate scopes and good functional group tolerance, this reaction offers corresponding carboxylic acids in moderate to excellent yields.

ChemInform Abstract: Quinonediimines as Redox‐Active Organocatalysts for Oxidative Coupling of Aryl‐ and Alkenylmagnesium Compounds under Molecular Oxygen.

It is revealed that N,N′-diphenyl-p-benzoquinonediimine works as a redox-active organocatalyst for the oxidative homo-coupling of aryl- and alkenylmagnesium compounds under molecular oxygen. The catalytic cycle was formally monitored by 1H NMR experiments.

Quinonediimines as redox-active organocatalysts for oxidative coupling of aryl- and alkenylmagnesium compounds under molecular oxygen.

It is revealed that N,N'-diphenyl-p-benzoquinonediimine works as a redox-active organocatalyst for the oxidative homo-coupling of aryl- and alkenylmagnesium compounds under molecular oxygen. The catalytic cycle was formally monitored by (1)H NMR experiments.

Bioconversion of substituted naphthalenes and β-eudesmol with the cytochrome P450 BM3 variant F87V

Bioconversion of various substituted naphthalenes that contain 1-methoxy- and 1-ethoxy-naphthalenes, methylnaphthalenes, dimethylnaphthalenes, and naphthalenecarboxylic acid methyl esters were performed using recombinant Escherichia coli cells, which expressed the gene coding for a cytochrome P450 BM3 variant F87V (P450 BM3 (F87V)) that was N-terminally fused to an archaeal peptidyl-prolyl cis-trans isomerase. In addition, bioconversion experiments with the same substrates were carried out using those that expressed the phnA1A2A3A4 genes for a polycyclic aromatic hydrocarbon (PAH)-dihydroxylating dioxygenase, which originated from a PAH-utilizing marine bacterium Cycloclasticus sp. strain A5. Consequently, a variety of mono-hydroxylated derivatives were generated from these substituted naphthalenes. Oxidative aryl coupling was found to produce a novel compound 4,4'-diethoxy-[2,2']-binaphthalenyl-1,1'-diol from 1-ethoxynaphthalene with the E. coli cells expressing the P450 BM3 (F87V) gene. This recombinant E. coli was further shown to introduce the hydroxyl group regio- and stereo-specifically into a sesquiterpene β-eudesmol.

ChemInform Abstract: CuCl-Mediated Intramolecular Oxidative Coupling of Aryl- and Alkenyltrimethylstannane Functions.

ChemInform 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.

Highly Effective and Diastereoselective Synthesis of Axially Chiral Bis-sulfoxide Ligands via Oxidative Aryl Coupling

A series of axially chiral bis-sulfoxide ligands have been efficiently synthesized via oxidative coupling with high diastereoselectivities. The axial chirality is well controlled by the tert-butylsulfinyl or the p-tolylsulfinyl group. These axially chiral bis-sulfoxides proved to be remarkably efficient ligands for the rhodium-catalyzed asymmetric 1,4-addition of arylboronic acids to 2-cyclohexenone with 99% ee.

Synthesis of C2-symmetrical diamine based on (1 R)-(+)-camphor and application to oxidative aryl coupling of naphthols

The new C 2-symmetrical 1,2-diamine { N, N′-bis[(1 R,2 R,4 R)-1,7,7-trimethylbicyclo[2.2.1]hept-2-yl]-1,2-ethanediamine} 3 has been synthesized from commercial (1 R)-(+)-camphor 1 and scrutinized as ligand in the oxidative biaryl coupling of naphthol derivatives. Under the optimal conditions employing a Cu(I)- 3 triflate complex (10 mol%) in dichloroethane–MeCN and molecular sieves with air as the oxidant, aryl coupling of naphthol derivatives could be achieved in satisfactory yields (48–90% yield) and ees of up to 65%. The ester moiety at the 3-position of the substrate was found to be crucial for a satisfactory asymmetric induction in the present coupling reaction.

ChemInform Abstract: Novel Concepts in Directed Biaryl Synthesis. Part 88. Oxidative Aryl Coupling Reactions: A Biomimetic Approach to Configurationally Unstable or Axially Chiral Biaryl Natural Products and Related Bioactive Compounds.

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.

Oxidative aryl coupling reactions: a biomimetic approach to configurationally unstable or axially chiral biaryl natural products and related bioactive compounds

Phenolic and non-phenolic oxidative aryl coupling reactions were successfully used in the efficient synthesis of diverse natural products and related compounds in the fields of biphenyls, biscarbazoles and bisnaphthylisoquinolines. For sterically more hindered biaryls, which consequently show the phenomenon of axial chirality, the products were prepared in an atropisomerically pure form. Their absolute axial configurations were assigned mainly by experimental and computational CD investigations.

CuCl-mediated intramolecular oxidative coupling of aryl- and alkenyltrimethylstannane functions

[reaction: see text] The syntheses of bis-trimethylstannanes 8, 10, 12-14, 16, 18, 21, and 22 are described. Treatment of these substances with approximately 5 equiv of CuCl in DMF at rt for 30-60 min effects, in each case, oxidative coupling between the two sp2 carbon centers bearing the Me3Sn function to produce good-to-excellent yields of tricyclic products 23-31, respectively.

Oxidation by Iron(III) Complexes. VIII. The Reactions of Iron(III) Chloride with Toluene and Substituted Toluenes

Abstract The thermal and photochemical reactions of toluene with anhydrous iron(III) chloride in the solid state result in nuclear chlorination. In a homogeneous system, a side-chain reaction occurs under irradiation with light, although no product is obtained in the thermal reaction. The addition of water to the iron(III) chloride–toluene system in the range of the molar ratio of 1–5 changes the course of the photochemical reaction; in the water/iron(III) chloride molar ratios of 1–1.7, 3, and 4–5, the main products are the diphenylmethane-type compound, o- or p-chlorotoluene (o>p), and benzyl chloride respectively. Pyridine as a ligand acts to give benzyl chloride selectively. The Mössbauer data of the FeCl3/nH2O solid show that the arrangement of the Cl− ion around the Fe(III) ion changes upon the addition of water. The thermal and photochemical reactions of p-methoxytoluene with anhydrous iron(III) chloride give 2,2′-dimethoxy-4,4′-dimethylbiphenyl by oxidative aryl coupling. Water inhibits the aryl coupling reaction.