A General, Highly Efficient Ullmann C-O Coupling Reaction under Microwave Irradiation and the Effects of Water

A general, rapid and highly efficient method for the synthesis of diaryl ethers under the assistance of microwave irradiation was described. A series of diaryl ethers were prepared by direct coupling of phenols and aryl halides in good to excellent yields in anhydrous DMF or NMP at 150 ℃ within 20 rain. The presence of water was found to have a significant impact on the Ullmann C-O coupling reaction between aryl halides and phenols under microwave irradiation.     

Iodine-catalyzed N-sulfonylation of benzotriazoles with sodium sulfinates under mild conditions

A new and convenient procedure is developed for the preparation of N-sulfonylbenzotriazoles from sodium sulfinates and benzotriazoles using molecular iodine as catalyst via the S–N bond formation reaction. This catalytic radical sulfonylation proceeds efficiently in air at room temperature under neutral conditions, and in short reaction time, to afford the corresponding N-sulfonylbenzotriazoles in good yields, thus extending the catalytic application of molecular iodine in organic synthesis.     

Microwave-assisted synthesis of α-hydroxy aromatic ketones from α-bromo aromatic ketones in water

A reaction ofα-bromo aromatic ketones in water with microwave irradiation gave the correspondingα-hydroxy aromatic ketones in good yields.The use of microwaves was found to significantly improve yields and shorten the reaction time.This reaction afforded a very clean,convenient method for the synthesis ofα-hydroxy aromatic ketones.     

Iodine Catalyzed Microwave-Assisted Synthesis of 14-Aryl（Alkyl）-14H-dibenzo[a,j]xanthenes

A straightforward and effective procedure for the synthesis of 14-aryl（alkyl）-14H-dibenzo[aj]xanthenes was described using a catalytic amount of molecular iodine under microwave irradiation to afford the corresponding xanthenes in good yields.     

Stereodivergent Synthesis of a-Aminomethyl Cinnamyl Ethers via Photoredox-Catalyzed Radical Relay Reaction

A photocatalytic multi-component radical relay reaction has been developed for the stereodivergent synthesis of both stereoisomers of α-aminomethyl cinnamyl ethers.The radical relay reaction of hydroxylamine derivatives,enol ethers and alkenyl boronic acids in DMSO under white LEDs could lead to E-isomers of α-aminomethyl cinnamyl ethers.The E-isomers could subsequently isomerize to less thermodynamically stable Z-isomers under blue LEDs using toluene as-the co-solvent in a one-pot manner.     

Microwave-assisted base-free synthesis of trans-cinnamic acids using hypervalent iodonium salts

A fast and convenient base-free Heck reaction of acrylic acid with hypervalent iodonium salts was achieved under microwave irradiation in water, providing a simple method for the synthesis of trans-cinnamic acids in good yields in short time.     

Radical cation salts induced domino reaction of anilines with enol ethers:Synthesis of 1,2,3,4-tetrahydroquinoline derivatives

A domino reaction of anilines with cyclic and acyclic enol ethers induced by catalytic amounts of TBPA^·+（5 mol%） was investigated and a series of 2,4-disubstituted-1,2,3,4-tetrahydroquinolines were synthesized.Different from cyclic enol ethers, when acyclic enol ethers were used in the reaction,they serve as surrogates of acetaldehyde,producing a series of 2-methyl-4- anilino-1,2,3,4-tetrahydroquinolines.A single electron transfer mechanism was proposed to rationalize the products formation.     

An efficient and mild protocol for the synthesis of unsymmetrical ureas in the absence of catalyst and additives

<正>A new practical method for the synthesis of unsymmetrical ureas was achieved by reaction of phenylurea with primary and secondary amines under neutral and mild condition in very good yields.The reaction took place in refluxing dioxane and does not require any catalyst or additives.     

An environmentally benign benzylic oxidation catalyzed by hypervalent iodine intermediate in water

An effective and environmentally benign benzylic oxidation for transition of alkylarenes into the corresponding carbonyl compounds was reported.Alkylarenes were mixed and stirred with potassium bromide,m-chloroperbenzoic acid and a catalytic amount of iodobenzene in water at 60 8C for several hours,a series of the corresponding carbonyl compounds was obtained in moderate to good yields.In the reaction,iodobenzene was first oxidized by m-chloroperbenzoic acid into the hypervalent iodine intermediate which then reacted with potassium bromide to form the key radical initiator for the benzylic oxidation.     

Copper-catalyzed Ullmann-type synthesis of diaryl ethers assisted by salicylaldimine ligands

A series of salicylaldimine ligands were designed to promote the copper-catalyzed Ullmann cross- coupling reaction. After a screening process, 2-（（2-isopropylphenylimino）methyl）phenol was found to serve as a good supporting ligand for this reaction. Employing this Schiff-base ligand as a new supporting ligand, the copper-catalyzed coupling reactions of aryl bromides and aryl iodides with various phenols successfully proceeded in good yields under mild conditions. Various diaryl ethers were obtained with excellent yields in dioxane in the presence of K3P04 and a catalytic amount of copper（I） salt.     

Iodine-promoted imino-Diels-Alder reaction of fluorinated imine with enol ether: synthesis of 2-perfluorophenyl tetrahydroquinoline derivatives

Iodine was used to catalyze the hetero-Diels-Alder reaction of pentafluorobenzylidineaniline (C₆F₅CHNAr 1) with enol ethers to afford the corresponding tetrahydroquinolines derivatives as a mixture of cis/trans stereoisomers in moderate yields. These products could also be prepared by one-pot, three-component reaction of pentafluorophenylaldehyde, anilines, and enol ethers under the same reaction condition. Mild and neutral reaction conditions, facile experimental procedure, and low price of iodine should make this method attractive for practical synthesis of many fluorinated tetrahydroquinoline derivatives.     

Synthesis of 2-arylacrylic esters from aryl methyl ketones via Wittig reaction/singlet oxygen ene reaction

An efficient synthetic method has been developed for the synthesis of 2-arylacrylic esters from the corresponding aryl methyl ketones via Wittig reaction and singlet oxygen ene reaction. Wittig reaction to aryl methyl ketones with (methoxymethyl)triphenylphosphonium chloride in basic condition afforded the methyl enol ethers, and then 2-arylacrylic esters were obtained by singlet oxygen ene reaction, followed by tosylation and elimination in one-pot to the methyl enol ethers in good yields.     

Intramolecular construction of trifluoromethyl group by the palladium-catalyzed reaction of 2,3,3-trifluoroallylic carbonates with O-nucleophiles

The synthesis of the trifluoromethyl group containing enol ethers by the palladium-catalyzed intermolecular reaction of 2,3,3-trifluoroallylic carbonates with oxygen nucleophiles was accomplished. The reaction proceeds through the intermolecular attack of oxygen nucleophiles on the C-2 carbon atom of the allylic unit, and the intramolecular fluorine atom shift from the C-2 position to the C-3 position. The reactions with several types of alcohols and phenols proceeded smoothly, and afforded the corresponding trifluoromethyl group containing enol ethers in good to high yields.     

Lewis base catalyzed Mannich-type reactions between trimethylsilyl enol ethers and aldimines

Lewis base catalyzed Mannich-type reaction between trimethylsilyl enol ethers and N-tosylaldimines is described. Nitrogen anions generated from amides or imides such as lithium benzamide or potassium phthalimide are found to be effective Lewis base catalysts in DMF at room temperature to afford the corresponding beta-amino carbonyl compounds in good to high yields; the oxygen anion generated from carboxylic acids such as lithium acetate was also found to be effective in dry DMF. The above-mentioned lithium acetate-catalyzed Mannich-type reaction between aldimines and various trimethylsilyl (TMS) enol ethers such as silyl ketene acetal proceeded smoothly even in water-containing DMF. Then, Lewis base catalyzed three-component Mannich-type reactions of TMS enol ether, tosylamide, and aromatic aldehyde having electron-withdrawing group such as p-nitrobenzaldehyde were investigated. The reaction proceeded smoothly to afford the corresponding beta-amino ester in good yield. Further, ammonium carboxylates such as tetrabutyl ammonium acetate or tetrabutyl ammonium benzoate were found to be more effective Lewis base catalysts in the above-mentioned Mannich-type reaction. The synthesis proceeded in various solvents at lower temperatures. The reaction between aldimines and TMS enol ethers generated from thioester and various ketones such as propiophenone or cyclohexanone also proceeded smoothly to afford the corresponding beta-amino carbonyl compounds in high yields with good to high anti-selectivities.     

Evaluation of C-trialkylsilyl enol and thioenol ethers as intermediates in the synthesis of acylsilanes

C-silyl enol ethers or thioenol ethers have been prepared by a Peterson reaction, as intermediates for acylsilane synthesis. Bis(trialkylsilyl)(methoxy)- or -(methylsulfanyl)methanes bearing identical or different trialkylsilyl groups were used as starting materials in order to assess the selectivity of the Peterson elimination step. A good selectivity was observed only with ethers bearing the TMS and TBDMS groups. However, there is no practical interest to use such reagents owing to the difficulty to obtain them in correct yields. Bis(trimethylsilyl)(methylsulfanyl)methane proved to be a good reagent for the preparation of C-silyl thioenol ethers, which are hydrolyzed under classical acid conditions to give acylsilanes in fair overall yields. This convenient procedure was extended to the synthesis of bis(acylsilanes).     

Indium-mediated beta-allylation,beta-propargylation,and beta-allenylation onto alpha,beta-unsaturated ketones: reactions of in-situ-generated 3-tert-butyldimethylsilyloxyalk-2-enylsulfonium salts with in-situ-generated organoindium reagents

3-tert-Butyldimethylsilyloxyalk-2-enylsulfonium salts, generated in situ from the reaction of alpha,beta-enones with dimethyl sulfide in the presence of TBSOTf, underwent a novel nucleophilic substitution with allylindiums to give silyl enol ethers of delta,epsilon-alkenyl ketones in good yields, which correspond to formal Michael addition products. In a similar manner, 1,4-propargylation of propargylindiums onto the sulfonium salts produced the corresponding silyl enol ethers of delta,epsilon-alkynyl ketones in good yields. Organoindium reagents derived from gamma-substituted propargyl bromide and indium afforded the corresponding silyl enol ethers of beta-allenyl ketones in good yields. The reaction proceeds via an addition-substitution mechanism involving the formation of allylic sulfonium salts. The presence of the intermediate sulfonium salt was confirmed by observation of the low-temperature (1)H NMR spectra.     

1,4-silatropy of S-alpha-silylbenzyl thioesters: a convenient route to silyl enol and dienol ethers accompanied by C-C bond formation via thiocarbonyl ylides

A novel convenient method for the generation of thiocarbonyl ylides from readily accessible starting materials and the first synthetic application of in situ generated ylides in the synthesis of silyl enol and dienol ethers, accompanied by C-C bond formation, is described. Under completely neutral conditions without any catalyst or additive, thermal reactions of S-alpha-silylbenzyl thioesters in sealed tubes at 180 degrees C provided silyl enol and dienol ethers in good to excellent yields with high stereoselectivities. This procedure consists of a multistep reaction in a one-pot process, i.e., 1,4-silatropy of S-alpha-silylbenzyl thioesters to give thiocarbonyl ylides, 1,3-electrocyclization of the ylides to give thiiranes, and the extrusion of sulfur from thiiranes to give silyl enol and dienol ethers.     

A highly efficient synthesis of 1,2,3,4-tetrahydroquinolines by molecular iodine-catalyzed domino reaction of anilines with cyclic enol ethers

A highly efficient method for the synthesis of 1,2,3,4-tetrahydroquinoline derivatives via a molecular iodine catalyzed domino reaction of anilines with cyclic enol ethers, such as 2,3-dihydrofuran and 3,4-dihydro-2H-pyran, is described. The reaction may proceed through an aza-Diels-Alder process between an in situ generated 2-azadiene and another equivalent of cyclic enol.     

Gold-catalyzed hydrosilyloxylation driving tandem aldol and mannich reactions

The chemoselective formation of an enolate from alkyne in the presence of a carbonyl and imine group was realized, which constructed a variety of structural motifs under exceedingly mild reaction conditions in a tandem process. Reaction driving tandem hydrosilyloxylation/aldol reactions was achieved through the formation of enol silyl ethers catalytically generated in situ from readily available alkynes. These reactions were expanded to obtain β-amino enol silyl ethers in good yields via the tandem hydrosilyloxylation/isomerization/Mannich reaction.     

Easy access to CF2-containing molecules based on the reaction of 2,2,3,3-tetrafluorooxetane with various nucleophiles

2,2,3,3-Tetrafluorooxetane reacted easily with organolithium reagents to give 1,1,3-trisubstituted 2,2-difluoropropan-1-ols in good to excellent yields. On the other hand, the reaction with Grignard reagent led to 3-bromo-1,1-disubstituted 2,2-difluoropropan-1-ols in good yields. On treating with lithium enolates, generated from enol silyl ethers and MeLi/LiBr, the corresponding 1-bromo-2,2-difluoro-3,5-dicarbonyl compounds were obtained in fair to good yields. 3-Iodo-2,2-difluoropropanoate, prepared readily from 2,2,3,3-tetrafluorooxetane and NaI, reacted successfully with various silyl enol ethers in the presence of a radical initiator to provide the corresponding coupling products in good yields.