Silica chloride: An efficient promoter for oxidation of arylboronic acids to phenols

This work reports simple, highly efficient protocol for the oxidation of arylboronic acids. Various arylboronic acids were selectively and completely converted into their corresponding oxidized phenols using H₂O₂ as an oxidant in presence of catalytic amount of silica chloride. The results show that silica chloride is a suitable and efficient promoter for the oxidation of arylboronic acids. Heterogeneous catalyst, mild reaction conditions, easy availability of the reagent, easy work-up, excellent yield of corresponding phenols, short reaction time and broad substrate scope makes this protocol attractive and a practical alternative to the existing methods.     

In situ generated cationic Pd(II)/bipyridine-catalyzed addition of arylboronic acids to N-sulfonyl-arylaldimines

An in situ generated cationic Pd(II)/bipyridine-catalyzed nucleophilic addition of arylboronic acids to N-sulfonyl arylaldimines was developed and optimized, and the reaction was proceeded highly efficiently and conveniently in CH₃NO₂. A series of arylboronic acids and N-sulfonyl arylaldimines were surveyed, and 12 of 13 examples gave 90～96% yields.     

低温Suzuki反应合成联苯及三联苯化合物

发展了一个低温下无配体钯催化溴代芳烃与芳基硼酸的Suzuki反应体系。该体系以醋酸钯为催化剂,无水碳酸钾为碱,乙醇水溶液为溶剂,无需加入任何配体,在0oC下即可高效催化溴代芳烃与芳基硼酸的Suzuki反应;反应的底物容忍性好,产品分离收率最高达97%。以溴代芳基N-甲基亚氨基二乙酸硼酸酯为砌块分子,通过调控反应温度,实现了砌块分子选择性Suzuki反应,从而一锅合成了不对称三联苯化合物,产品收率最高为81%。     

SiO2-NHC-CuI–Catalyzed N-Arylation of Imidazoles with Arylboronic Acids Under Base-Free Reaction Conditions

N-Arylation of imidazoles with arylboronic acids was efficiently carried out in the presence of a catalytic amount of SiO₂-NHC-Cu^I in methanol at room temperature under base-free reaction conditions. The reactions of a variety of arylboronic acids with imidazoles generated the corresponding products N-arylimidazoles in good to excellent yields. In addition, SiO₂-NHC-Cu^I could be recovered and recycled for six consecutive trials without significant loss of its reactivity.     

Solvent‐Free,Palladium‐Catalyzed Suzuki–Miyaura Cross‐Couplings of Aryl Chlorides with Arylboronic Acids

Pd(MeCN)₂Cl₂/PCy₃ was found to be an efficient catalytic system for the Suzuki–Miyaura cross‐couplings of aryl chlorides with arylboronic acids under solvent‐free conditions. Furthermore, the presence of the conventional solvents had deleterious effect on the reaction. In the presence of Pd(MeCN)₂Cl₂, PCy₃, and TBAF (tetra‐n‐butylammonium fluoride), a number of aryl chlorides including heteroaryl chlorides were coupled with arylboronic acids or heteroarylboronic acids smoothly to afford the corresponding products in moderate to excellent yields.     

Nickel(II)-catalyzed addition reaction of arylboronic acids to isatins

A Ni-catalyzed addition of arylboronic acids to isatins was first developed. The reaction, driven by Ni(acac)₂ and dppp as the phosphine ligand, gave 3-aryl-3-hydroxy-2-oxindoles in up to 97% yield. Scopes of benzyl-protected isatins and arylboronic acids were examined. Substituted phenylboronic acids along with fused-ring and heterocyclic boronic acids reacted with isatins smoothly. Preliminary asymmetric catalysis was investigated as well, showing moderate enantioselectivity. The mechanism was also described.     

pH‐Dependent conjugate addition of arylboronic acids to α,β‐unsaturated enones catalyzed by a reusable palladium(II)/cationic 2,2′‐bipyridyl system in water under air

A reusable Pd(NH₃)₂Cl₂/cationic 2,2′‐bipyridyl system for the catalysis of the conjugate addition of arylboronic acids to α,β‐unsaturated enones in water under air was developed. Addition of arylboronic acids to both cyclic and acyclic enones progressed smoothly, providing the products in good to high yields, the best result being obtained when HBF₄ was used to adjust the pH value to 1.0. After the reaction, the residual aqueous solution could be reused several times, making the reaction greener and reducing wastage of precious metals. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis of Aryl Ketones by Cross-Coupling Reaction of Arylboronic Acids with Carboxylic Anhydrides in Aqueous Phase

A highly efficient aqueous system of PdCl₂-catalyzed cross-coupling reaction of arylboronic acid with carboxylic anhydride (Suzuki-type reaction) without the use of phosphine ligands was developed. The reactions went smoothly in acetone/H₂O phase to give good yields of aryl ketones in short reaction times (1–3 h) at room temperature in air and were unaffected by the presence of electron-releasing and electron-withdrawing substituents in both the arylboronic acids and carboxylic anhydrides.     

Rh(I)/diene-catalyzed addition reactions of aryl/alkenylboronic acids with aldehydes

[Rh(COD)Cl]₂-catalyzed addition reactions of arylboronic acids with aldehydes, with low Rh(I) catalyst loading, are described. We also found that the reaction of arylboronic acids with α,β-unsaturated aldehydes greatly depends on the solvent and the steric hindrance of the reagents/substrates.     

Nickel‐Catalyzed Mizoroki–Heck‐ versus Michael‐Type Addition of Organoboronic Acids to α,β‐Unsaturated Alkenes through Fine‐Tuning of Ligands

Various arylboronic acids reacted with activated alkenes in the presence of [Ni(dppe)Br₂], ZnCl₂, and H₂O in CH₃CN at 80 °C to give the corresponding Mizoroki–Heck‐type addition products in good to excellent yields. Furthermore, 1 equivalent of the hydrogenation product of the activated alkene was also produced. By tuning the ligands of the nickel complexes and the reaction conditions, Michael‐type addition was achieved in a very selective manner. Thus, various p‐ and o‐substituted arylboronic acids or alkenylboronic acid reacted smoothly with activated alkenes in CH₃CN at 80 °C for 12 h catalyzed by Ni(acac)₂, P(o‐anisyl)₃, and K₂CO₃ to give the corresponding Michael‐type addition products in excellent yields. However, for m‐substituted arylboronic acids, the yields of Michael‐type addition products are very low. The cause of this unusual meta‐substitution effect is not clear. By altering the solvent or phosphine ligand, the product yields for m‐substituted arylboronic acids were greatly improved. In contrast to previous results in the literature, the present catalytic reactions required water for Mizoroki–Heck‐type products and dry reaction conditions for Michael‐type addition products. Possible mechanistic pathways for both addition reactions are proposed.     

氯化钯在氟化四丁基铵中当场生成纳米钯：一种高效、可回收的催化体系，在无配体和无溶剂条件下催化Suzuki-Miyaura反应

氯化钯在氟化四丁基铵中当场生成纳米钯,该钯催化剂在Suzuki-Miyaura交叉偶联反应中显示很高的催化效率。在氯化钯和氟化四丁基铵存在下,许多芳基卤代烃可以顺利与芳基硼酸发生偶联反应,得到中等到高的产率。此外,在Suzuki-Miyaura偶联反应中该氯化钯/氟化四丁基铵催化体系可以回收重复使用多次,并且芳基溴代烃可以在15-60分钟内反应完全。值得指出的是,该反应是在无溶剂、无配体和催化体系可回收重复使用的条件下进行的。这和无配体条件下TBAB中钯催化卤代芳烃与芳基硼酸的Suzuki-Miyaura交叉偶联反应方法。该氯化钯/氟化四丁基铵催化反应的反应机理也进行了讨论。     

Use of cheaper metal than Rh, CHCl3-free Pd catalyst, in 1,2-addition of aromatic aldehydes with arylboronic acids

Pd(OAc)₂-(±)-tol-BINAP-catalyzed arylation reaction of aromatic aldehydes with arylboronic acids in the absence of CHCl₃ is described.     

A nickel precatalyst for efficient cross-coupling reactions of aryl tosylates with arylboronic acids: vital role of dppf

An air-stable and easy-to-handle nickel precatalyst, (9-phenanthrenyl)Ni(II)(PPh₃)₂Cl, was examined for the cross-coupling reactions of aryl tosylates with arylboronic acids. Under the optimized reaction conditions, the catalytic system tolerates a wide range of activated, neutral and deactivated substrates. The selectivity of this cross-coupling reaction towards aryl tosylates and arylboronic acids has been investigated. It is proposed that ligand 1,1′-bis(diphenylphosphino)ferrocene (dppf) plays a key role in the coupling by enforcing a cis geometry in key intermediates and the active Ni(0) species.     

Electrophilic ipso-iodination of silylated arylboronic acids

Silylated functionalized arylboronic acids were converted into corresponding iodinated arylboronic acids in good yields via the electrophilic ipso-desilylation effected with iodine chloride in refluxing CHCl₃. Disilylated arylboronic acids were susceptible to diiodination. In addition, the structural characterization and reactivity of a novel sterically hindered ortho-silylated diarylborinic ester were reported. The potential of selected iodinated phenylboronic acids as monomers for the Suzuki-Miyaura cross-coupling polymerization was demonstrated.     

Recyclable and reusable Pd(OAc)2/PPh3/PEG‐2000 system for homocoupling reaction of arylboronic acids under air without base

A stable and efficient Pd(OAc)₂/PPh₃/PEG‐2000 catalytic system for homocoupling of arylboronic acids has been developed. In the presence of Pd(OAc)₂ and PPh₃, the homocoupling reaction of arylboronic acids was carried out smoothly in PEG‐2000 at 70 °C under air without base to afford a variety of symmetric biaryls in good to excellent yields. The isolation of the products was readily performed by extraction with diethyl ether, and the Pd(OAc)₂/PPh₃/PEG‐2000 system could be easily recycled and reused six times without significant loss of catalytic activity. Copyright © 2014 John Wiley & Sons, Ltd.     

One-pot synthesis of fluorinated terphenyls by site-selective Suzuki-Miyaura reactions of 1,4-dibromo-2-fluorobenzene

The Suzuki-Miyaura reaction of 1,4-dibromo-2-fluorobenzene with two equivalents of arylboronic acids gave fluorinated para-terphenyls. The reaction with 1 equiv of arylboronic acid resulted in site-selective formation of biphenyls. The one-pot reaction of 1,4-dibromo-2-fluorobenzene with two different arylboronic acids afforded fluorinated para-terphenyls containing two different terminal aryl groups.     

Palladium-catalyzed synthesis of arylacetamides from arylboronic acids

Aryl amides were synthesized by the palladium catalyzed cross-coupling reaction of α-bromoacetamides with arylboronic acids in good yields. Both electron-donating and electron-withdrawing substituents on the aromatic ring are found to be compatible. The addition of Cu₂O and PPh₃ was found to be essential for good reaction yields.     

Room temperature multicomponent synthesis of diverse propargylamines using magnetic CuFe2O4 nanoparticle as an efficient and reusable catalyst

We report the magnetic recoverable catalyst (CuFe₂O₄) catalyzed multicomponent reaction of aliphatic amines, formaldehyde, arylboronic acids and alkynyl carboxylic acids for the synthesis of diverse propargylamines at room temperature.     

Pd-catalysed conjugate addition of arylboronic acids to <Emphasis Type="Italic">α,β</Emphasis>-unsaturated ketones under microwave irradiation

The Pd-catalysed conjugate addition of arylboronic acids to α,β-unsaturated cyclic ketones was studied under controlled microwave irradiation conditions. A variety of catalysts, bases and solvents was explored in order to achieve optimum yields in the shortest possible reaction time. Under optimised conditions (Pd(OAc)₂/2,2′-bipyridine and KF in a mixture of toluene, water, and acetic acid and 10 min microwave irradiation), a range of arylboronic acids was successfully added to several cyclic enones. With chiral phosphane ligands, a promising enantioselectivity was obtained (85 % ee).     

An efficient and simple protocol for a PdCl2-ligandless and additive-free Suzuki coupling reaction of aryl bromides

A highly efficient, convenient, and environmentally friendly protocol was developed for the PdCl₂-catalyzed ligandless and additive-free Suzuki reaction of aryl bromides with arylboronic acids in water/ethanol.