Cross-coupling Of Aryl Iodides Research Articles

Cross Coupling of Aryl Iodides with Terminal Alkynes, Catalyzed by a PdCl2–Hydrophilic Arylphosphine Ligand System

Cross Coupling of Aryl Iodides with Terminal Alkynes, Catalyzed by a PdCl2–Hydrophilic Arylphosphine Ligand System

Mizoroki-Heck carbon-carbon cross-coupling reactions by water-soluble palladium (II) complexes in neat water

Water-soluble palladium complexes were synthesized, characterized, tested as (pre)catalyst for Mizoroki-Heck carbon-carbon cross-coupling reactions in water. Cross-coupling of aryl iodides and bromides with methyl and ethyl acrylates was achieved at 140 °C. When styrene was employed as the substrate excellent conversion to trans-stilbene was observed using 5 mol% catalyst loading in the presence of TBAB. The catalysts are versatile and can couple various substrates in a non-toxic and benign solvent. After extraction of the organic product the catalyst containing aqueous layer could be recycled twice with a significant drop in the aryl halide conversion after the third recycle. No catalyst poisoning was observed in the mercury poisoning experiments with both catalysts and this proves that both catalytic systems function as molecular homogeneous catalysts.

Asymmetric Reductive Cross-Coupling of Aryl Iodides with α-Chloroboranes by Nickel/Photoredox Catalysis

Asymmetric Reductive Cross-Coupling of Aryl Iodides with α-Chloroboranes by Nickel/Photoredox Catalysis

New biomaterials for Ni biosorption turned into catalysts for Suzuki-Miyaura cross coupling of aryl iodides in green conditions.

In parallel with increasing Ni production and utilisation, Ni pollution in the soil–water continuum has become an alarming and global problem. Solutions for removing Ni from industrial effluents have been widely investigated and biosorption has emerged as an efficient, cost-effective, scalable and sustainable alternative for water treatment. However, the biosorption capacity is limited by the chemical composition of the biomaterial and the Ni-enriched biomaterials are rarely valorised. In this work, the biosorption capacity of three abundant biomaterials with different chemical properties – water hyacinth, coffee grounds and pinecones – was studied before and after functionalization, and reached a maximum biosorption capacity of 51 mg g−1 of Ni(ii). A bioinspired functionalization approach was investigated introducing carboxylate moieties and was conducted in green conditions. The Ni-enriched biomaterials were valorised by transformation into catalysts, which were characterised by MP-AES and XRPD. Their characterisation revealed a structure similar to nickel formate, and hence the Eco-Ni(HCOO)2 catalysts were tested in Suzuki–Miyaura reactions. Several aryl iodides were successfully cross-coupled to phenylboronic acids using Eco-Ni(HCOO)2 without any ligand, a mild and green base in a mixture of green solvents.

Palladium-Catalyzed Cross-Coupling of Ethyl Bromodifluoroacetate with Aryl Bromides or Triflates and Cross-Coupling of Ethyl Bromofluoroacetate with Aryl Iodides.

A palladium-catalyzed Negishi cross-coupling reaction of ethyl bromodifluoroacetate with aryl bromides or aryl triflates to construct C(sp2)-CF2 bonds is described. The reaction was conducted under mild reaction conditions, and no preparation of organozinc reagents is required. This is the first report encompassing the conversion of aryl triflates into products containing C-CF2 bonds. In addition, the construction of C(sp2)-CHF bonds was achieved under mild conditions via a cross-coupling of aryl iodides with ethyl bromofluoroacetate.

Copper-Catalyzed Oxirane-Opening Reaction with Aryl Iodides and Se Powder.

Using Se powder as the selenating reagent, the copper-catalyzed double C-Se cross-coupling of aryl iodides, epoxides, and elemental selenium has been developed. This strategy provides a straightforward approach to the synthesis of β-hydroxy phenylselenides with excellent regioselectivity of the ring opening reaction. This process proceeds in generally good yields and is compatible with a broad range of functional groups.

Rhodium-catalyzed triarylphosphine synthesis via cross-coupling of aryl iodides and acylphosphines

Rhodium(I)-catalyzed C–P cross-coupling reaction with aryl iodides and acylphosphines was disclosed for a straight forward synthesis of triarylphosphines. The acylphosphines were successfully employed as both the phosphorus source and the ligand to the Rh(I) catalyst. The triarylphosphines could be afforded in a yield up to 98% with good toleration of wide functional groups.

ChemInform Abstract: A Highly Efficient Copper and Ligand Free Protocol for the Room Temperature Sonogashira Reaction.

AbstractThe protocol is equally efficient for cross coupling of aryl iodides with aryl acetylenes or aliphatic alkynes at room temperature.

An insight into the synthesis of novel aryl-substituted alicyclic β-amino acid derivatives through substrate-directed palladium-catalysed regio- and stereoselective cross-coupling

Novel aryl-substituted alicyclic β-amino acid derivatives were synthesized through substrate-determined palladium-catalysed cross-coupling of aryl iodides with five- or six-membered cycloalkene β-amino esters.

Graphene-supported Cu2O nanoparticles: an efficient heterogeneous catalyst for C–O cross-coupling of aryl iodides with phenols

Cu2O/graphene as a heterogeneous catalyst can efficiently catalyze the C–O cross-coupling of aryl iodides with phenols.

Magnetically-recoverable Pd-immobilized layered double hydroxide–iron oxide nanocomposite catalyst for carbon–carbon cross-coupling reactions

A novel magnetic composite catalyst has been prepared by immobilizing a palladium(0) complex, Pd 2 (dba) 3 , onto Mg–Al-layered double hydroxide shell supported on magnetite core. This new catalyst was characterized by XRD, TEM, EDX, FTIR, XPS, thermogravimetry and microanalytical techniques and magnetometric measurements. The performance of the catalyst was tested in the Heck and Suzuki reactions and confirmed to be efficient in the cross-coupling of aryl iodides under mild conditions. A novel catalytic system active in the Heck-Mizoroki and Suzuki-Miyaura reactions is reported. The system is prepared by incorporating Pd 2 (dba) 3 to a Mg-Al-LDH shell supported on magnetite core. The magnetically recoverable catalyst exhibited moderate activity with aryl iodides in carbon-carbon cross-coupling reactions. ► Pd 2 (dpa) 3 was immobilized on Mg–Al–LDH shell supported on magnetite core. ► The magnetically recoverable nanocomposite catalyst displayed soft ferromagnetism. ► Pd-LDH@M moderately catalyzed cross-coupling reactions of aryl iodides.

ChemInform Abstract: Aminoborylation/Suzuki—Miyaura Tandem Cross Coupling of Aryl Iodides as Efficient and Selective Synthesis of Unsymmetrical Biaryls.

AbstractSequential borylation of a first aryl iodide (I) using a dialkylaminoborane followed by a Suzuki—Miyaura cross coupling of second aryl iodide (II) affords unsymmetrical biaryls, in an efficient and practical manner.

Aminoborylation/Suzuki–Miyaura tandem cross coupling of aryl iodides as efficient and selective synthesis of unsymmetrical biaryls

Sequential borylation of a first aryl iodide using a dialkylaminoborane followed by a Suzuki-Miyaura cross coupling of second aryl iodide ended up with an efficient, selective and practical synthesis of unsymmetrical biaryls. This tandem coupling shows a wide range of applicability.

Pd(OAc)2-Catalyzed Carbonylative Coupling of Aryl Iodide with Ortho-Haloamines in Water

The carbonylative cross coupling of aryl iodide with ortho-haloaniline to ortho-haloanilide using phosphine-free Pd(OAc)2 catalyst in water as a reaction medium has been studied. The present protocol facilitated the reaction of o-haloanilines with a wide variety of hindered and functionalized aryl iodides, affording good yields of the desired products. The protocol was also extended for the synthesis of benzoxazoles through cyclization of ortho-haloanilide using Cu(acac)2 catalyst.

ChemInform Abstract: Effect of Counterions and Central Cores of Tripodal Imidazolium Salts on Palladium‐Catalyzed Suzuki—Miyaura Cross‐Coupling Reactions.

AbstractAmong a variety of benzene‐, nitrogen‐, or carbon‐centered tripodal imidazolium salts bearing different counterions, the benzene‐centered hexafluorophosphate salt (TIMB) shows the best activity as ligand in the Suzuki—Miyaura cross coupling of aryl iodides or bromides (I) with arylboronic acids (II).

ChemInform Abstract: An Efficient Copper‐Catalyzed Cross‐Coupling Reaction of Thiols with Aryl Iodides.

AbstractThe cross coupling of aryl iodides with a variety of aromatic and aliphatic thiols is efficiently catalyzed by inexpensive ligand‐free Cu2O.

Microwave‐Assisted Cross‐Coupling for the Construction of Diaryl Sulfides

AbstractThe construction of diaryl sulfides through the cross‐coupling of aryl iodides and thiols in microwave heating is described. By using this method, a variety of diaryl sulfides can be prepared in a mild condition and in high yields. Deactivated 4‐nitrothiophenol was effective to afford the product in 94% yield. Sterically hindered ortho‐substituted aryl iodides or thiophenols provided diaryl sulfides effectively by this microwave‐assisted coupling reaction.

Mechanistic Insights into C−S Cross-Coupling Reactions Catalyzed by Nickel Bis(phosphinite) Pincer Complexes

Nickel bis(phosphinite) pincer complexes [2,6-(R2PO)2C6H3]NiCl (R = Ph, 1a; R = Me, 1b; R = iPr, 1c; R = tBu, 1d) show catalytic activity in cross-coupling of aryl iodides and aryl thiols. The optimal catalytic conditions involve 1 mol % of 1a and 2 equiv of KOH (with respect to aryl thiols) in DMF at 80 °C and tolerate a variety of functional groups in the substrates. The potential intermediates in these catalytic reactions, such as nickel thiolate complexes [2,6-(Ph2PO)2C6H3]NiSAr (Ar = Ph, 2a; Ar = p-MeC6H4, 3a; Ar = p-MeOC6H4, 4a), have been synthesized and spectroscopically characterized. The reaction between 2a and PhI in DMF-d7 is slow enough to argue against 2a being directly involved in the C−S bond-forming step. NMR studies suggest that the pincer ligand framework in complexes 1a, 3a, and 4a is destroyed by KOH via the cleavage of P−O bonds to release Ph2POK, and further decomposition leads to Ph3P and other phosphorus-containing products. The cross-coupling reactions are more effectively cataly...

Efficient ligand-free nickel-catalyzed C–S cross-coupling of thiols with aryl iodides

NiCl 2·6H 2O efficiently catalyzes the C–S bond formation by the cross-coupling of aryl iodides with thiols in tetrabutylammonium bromide (TBAB) in excellent yield. The reaction functions in air and the NiLn-TBAB can be recovered and recycled without the loss of activity.

Sonogashira Cross-Coupling Using Carbon Aerogel Doped with Palladium Nanoparticles; A Recoverable and Reusable Catalyst

The Sonogashira cross coupling of aryl iodides with ter- minal alkynes has been carried out in the presence of carbon aero- gels doped with metallic palladium nanoparticles. Coupling products have been isolated in excellent yields and the catalyst sys- tem can be easily recovered in the presence of air without any par- ticular precautions and reused several times.