A practical method for preparation of phenols from arylboronic acids catalyzed by iodopovidone in aqueous medium

A novel and efficient strategy for the ipso-hydroxylation of arylboronic acids to phenols has been developed using inexpensive, readily available, air-stable water-soluble povidone iodine as catalyst and aqueous hydrogen peroxide as oxidizing agent. The reactions were performed at room temperature under metal-, ligand- and base-free condition in a short reaction time. The corresponding substituted phenols were obtained in moderate to good yields by oxidative hydroxylation of arylboronic acids in aqueous medium.     

Catalysis by Amberlite IR-120 resin: a rapid and green method for the synthesis of phenols from arylboronic acids under metal, ligand, and base-free conditions

A clean process has been developed for the ipso-hydroxylation of aryl and heteroaryl boronic acids to the corresponding phenols using commercially available and recyclable Amberlite IR-120 resin and aqueous hydrogen peroxide as an oxidizing agent. The ion-exchange sulfonic acid resin catalyst could be readily recycled by filtration and directly reused at least four times without any significant loss of activity.     

Facile syntheses of homoleptic diarylmercurials via arylboronic acids

A general procedure for the syntheses of diarylmercurials is presented. Reactions proceeded in isopropanol in the presence of a base and arylboronic acid. With one exception, all reactions proceeded in good to excellent yields, and this procedure was applicable to a variety of aromatic and heteroaromatic boronic acids. Products were characterized by multinuclear NMR spectroscopy and microanalysis, and investigated by DFT calculations. The structure of di(4-pyridyl)mercury (6) was further authenticated by X-ray crystallography. Combined with previous work on the formation of arylgold(I) complexes via arylboronic acids, this procedure may be generally useful for the arylation of late transition metals.     

Homocoupling of arylboronic acids catalyzed by simple gold salts

A range of arylboronic acids undergo a homocoupling reaction in the presence of catalytic amount of gold salts to yield symmetrical biaryls. Alkenylboronic acids, arylboronic esters, and arylborates also participate in the gold-catalyzed homocoupling reaction.     

Nickel salt-catalyzed addition reaction of arylboronic acids to aromatic aldehydes

Arylation reaction of aromatic aldehydes with arylboronic acids proceeded smoothly in the presence of a base and catalytic amount of a nickel salt, Ni(ClO₄)₂·6H₂O, in toluene/IPA = 5:1 or IPA to afford corresponding diarylmethanols in good to excellent yields.     

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.     

Palladium catalyzed synthesis of mandelate derivatives from arylboronic acids and glyoxylate hemiacetals

NHC-coordinated cyclometalated palladium(II) catalyzed addition of arylboronic acids to methyl 2-hydroxy-2-methoxyacetate gave corresponding various functionalized methyl mandelate derivatives in good yields.     

Highly enantioselective rhodium-catalyzed conjugate addition of arylboronic acids to enones at room temperature

The rhodium-phosphoramidite-catalyzed asymmetric conjugate addition of arylboronic acids to enones proceeds at room temperature using [Rh(OH)(cod)]₂ or [RhCl(cod)]₂/KOH as stable and readily available catalyst precursors.     

Palladium-catalyzed hydroarylation of alkynes with arylboronic acids

Reaction of symmetrical and unsymmetrical alkynes with arylboronic acids, using PdCl₂ as catalyst source and i-Pr₂NPPh₂ as ligand, afforded trisubstituted alkenes with regioselectivity in good to excellent yields without a common additional acetic acid. Its efficiency has been demonstrated by its good functional groups, high yield and crowded substrates.     

A mild conversion of arylboronic acids and their pinacolyl boronate esters into phenols using hydroxylamine

Hydroxylamine was found to be a mild reagent for conversion of arylboronic acids and their pinacolyl boronate esters into phenols. This procedure works on most arylboronic acids at room temperature, yielding phenols in moderate to good yields, and efficiently on arylboronates also yielding phenols in good yields.     

Green and controllable metal-free nitrification and nitration of arylboronic acids

A novel and green nitrating reagent has been developed for the nitrification and nitration of arylboronic acids,which can be controlled by the reaction conditions.The process provides an attractive alternative to the traditional nitration protocols.     

Copper-mediated N- and O-arylations with arylboronic acids in a continuous flow microreactor: a new avenue for efficient scalability

A continuous flow procedure has been elaborated for the copper(II)-mediated N- and O-arylation of a range of compounds with arylboronic acids using a commercial microreactor setup. The compounds could be continuously generated in good yields paving the way for efficient scalability.     

Palladium-catalyzed direct arylation of 4-hydroxycoumarins with arylboronic acids via C-OH bond activation

Operationally simple PdCl₂-catalyzed direct arylation of 4-hydroxycoumarins with arylboronic acids via C-OH bond activation under mild conditions is described, which gave rise to the corresponding 4-arylcouamrins in good to excellent yields.     

Cooperation of biopolymer chitosan with hydrogen peroxide for ipso-hydroxylation of arylboronic acids under green conditions

Oxidative hydroxylation of arylboronic acids to the corresponding phenolic compounds under metal- and base-free aerobic conditions is successfully demonstrated on a biopolymer support (chitosan or chitosan immobilized onto carbon nanotubes ([email protected])). Hydrogen peroxide, as an eco-friendly oxidant, is compatible with the biopolymer supports and provides hydroxylation products in an efficient manner. The [email protected] biopolymer support is particularly interesting for its potential recyclability.     

Preparation of phenolic compounds through catalyst-free ipso-hydroxylation of arylboronic acids

A novel method for the preparation of phenolic compounds through ipso-hydroxylation of the corresponding widely available arylboronic acid precursors is described. Through application of a novel PEG400-H₂O₂ reactant system, a variety of substituted phenols and other aromatic analogues have been prepared in excellent yields at room temperature in the absence of any catalyst.     

水促进的三组分PBM反应合成三级胺

首次报道了甲醛衍生的胺缩醛和芳基硼酸在水的促进下,可以在没有催化剂的条件下高效的合成三级胺.在此基础上建立了一种利用多聚甲醛,二级胺和芳基或杂环硼酸合成三级胺的高效合成方法.此反应条件温和,操作简单,具有很好的底物适应性,目标产物的收率最高可达93%.     

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.     

Palladium-benzimidazolium salt catalyst systems for Suzuki coupling: development of a practical and highly active palladium catalyst system for coupling of aromatic halides with arylboronic acids

Palladium-benzimidazolium salt catalyst systems have been studied for the Suzuki coupling. A different substitutent effect has been uncovered with respect to nitrogen substituents in the benzimidazolium salts from the palladium-imidazolium salt analogs. A practical and highly active palladium catalyst system, PdCl₂/N,N′-dibenzylbenzimidazolium chloride 2, has been identified for the Suzuki coupling of aromatic halides with arylboronic acids. The coupling of a wide array of aromatic halides with arylboronic acids with the PdCl₂-2 catalyst system gave good to excellent yields. The effective palladium loading could be as low as 0.0001 mol% and 0.01-0.1 mol% for iodide and bromide substrates, respectively. The coupling of unactivated aromatic chlorides with arylboronic acids also gave good results using Cs₂CO₃ as base with a 2 mol% palladium loading. The electronic factors from aromatic halides exert a significant influence on the Suzuki coupling catalyzed by the PdCl₂-2 system while the electronic effect from the arylboronic counterparts is negligible. The aromatic halides with modest steric hindrance could also couple smoothly with phenylboronic acids using the PdCl₂-2 catalyst system.     

Copper-catalyzed synthesis of aromatic carboxylic acids from arylboronic acids and acetyl acetate

A simple and efficient copper-catalyzed method for the synthesis of aromatic carboxylic acids in moderate to high yields with great functional-group compatibility in the substrates has been developed. The new method uses readily available arylboronic acids and acetyl acetate as the starting materials and inexpensive CuI as the catalyst.     

Triolborates: water-soluble complexes of arylboronic acids as precursors to iodoarenes

A facile synthesis of aryl and heteroaryl iodides from water-soluble complexes of aryl- and heteroarylboronic acids has been developed.