Ionic Liquids for the Chemical Recycling of Polymeric Materials and Control of Their Solubility.

Plastics are wonderful materials that have modernized our daily life; however, importance of effective recycling of plastics is gradually recognized widely. In this account, we describe our discovery of new and efficient methods for the chemical recycling of plastics using ionic liquids (ILs). Since the chemical recycling usually requires high temperature conditions to breakdown chemical bonds in polymeric materials, we thought that less-flammability and non-volatility of ionic liquids are the most suitable physical properties for this purpose.

Vicinal Difunctionalization of Alkenes Using Vinyl Triflates Leading to γ-Trifluoromethylated Ketones.

We report a new methodology for the synthesis of γ-trifluoromethylated ketones from alkenes and vinyl triflate bifunctional reagents. The reaction proceeds via the addition of a β-trifluoromethyl alkyl radical to a vinyl triflate, followed by β-cleavage. We also demonstrate a one-pot version of the reaction for the vicinal functionalization of alkenes from alkynes.

One-Pot Synthesis of CF-Substituted Vinyl Trifluoromethanesulfonamides from Imines and Trifluoromethanesulfonic Anhydride.

The one-pot triflation/radical trifluoromethylation/triflation of imines leading to CF-substituted vinyl trifluoromethanesulfonamides is described. The reaction proceeds via the radical trifluoromethylation of vinyl trifluoromethanesulfonamides as the key step. This reaction is suitable for a variety of imines that contain halogen atoms, electron-donating groups, or electron-withdrawing groups, leading to moderate to good yields.

Synthesis of 1-(1-Arylvinyl)pyridin-2(1)-ones from Ketones and 2-Fluoropyridine.

We describe a simple and efficient procedure for the synthesis of -vinyl-substituted pyridones from ketones and 2-fluoropyridine in the presence of trifluoromethane sulfonic anhydride, followed by a base treatment. Various ketones with electron-donating or electron-withdrawing groups at the benzene rings can be used in this reaction. A preliminary mechanistic study indicates that it is not very likely that both vinyl triflates and vinyl cations play major roles as intermediates in this transformation.

Redox-Neutral Tetrafluoroethylation of Aryl Alkynes with 1,1,2,2-Tetrafluoroethane Sulfonic Acid Leading to α-Tetrafluoroethylated Acetophenones.

The redox-neutral tetrafluoroethylation of alkynes with 1,1,2,2-tetrafluroroethanesulfonic acid (TFESA) and azobis(isobutyronitrile) (AIBN) proceeds via the formation of vinyl tetrafluoroethanesulfonates followed by a radical tetrafluoroethylation. Experimental and theoretical results support an intermolecular reaction.

Development of Water Solubility of 2-Phenylsulfanylhydroquinone Dimer Dye.

With the aim of developing a new fluorescence dye with enhanced photophysical properties, this study describes the modification of the 2-phenylsulfanylhydroquinone dimer to realize a new bioimaging molecule. The characteristics of the dimer were advanced by introducing tetraethylene glycol side chains to provide sufficient water solubility and a tether consisting of an -hydroxysuccinimide-terminated C6-carbon chain to attach bioactive molecules. Two derivatives containing two or three tetraethylene glycol side chains were designed and prepared, and the latter showed sufficient water solubility for biochemical applications.

Inverse Hydroboration of Imines with NHC-Boranes Is Promoted by Diphenyl Disulfide and Visible Light.

We describe a simple and efficient procedure for nucleophilic borylation of imines in the absence of a photoredox catalyst. Visible light irradiation of an acetonitrile solution of an imine, an NHC-borane, and diphenyl disulfide (10 mol %) provides various stable α-amino NHC-boranes in good yields. The reaction proceeds via addition of a nucleophilic boryl radical to an imine, followed by hydrogen abstraction from thiophenol, which is generated from NHC-borane and diphenyl disulfide.

Physicochemical and Structural Properties of a Hydrophobicity/Hydrophilicity Switchable Ionic Liquid.

Herein, we report the physicochemical and structural properties of a new solubility-switchable ionic liquid (IL) comprising the glycerammonium (GA) cation with a hydrophilic group, the GA cation attached to an acetal-based protective group [protected GA (PGA)], and bis(trifluoromethanesulfonyl)amide (TFSA). The interionic volumes () of the hydrophobic [PGA][TFSA] and hydrophilic [GA][TFSA] ILs were evaluated based on solution density, revealing weaker ion-ion interactions in these relative to conventional ILs. The [PGA][TFSA] and [GA][TFSA] also exhibit poor ion-conducting properties, with up to an order of magnitude lower ionic conductivity (σ) and self-diffusion coefficient (), as compared with conventional ILs.

Hydrodecyanation of Secondary Alkyl Nitriles and Malononitriles to Alkanes using DiMeImd-BH.

The decyanation of secondary aliphatic nitriles and the 2-fold decyanation of malononitriles leading to alkanes in the presence of 1,3-dimethylimidazol-2-ylidene borane (diMeImd-BH) are reported. These reactions proceed via a radical mechanism that involves the addition of a borane radical to the nitrile to form an iminyl radical, followed by cleavage of a carbon-carbon bond. Theoretical calculations suggest that the β-cleavage of these iminyl radicals, which affords NHC-BHCN and the corresponding alkyl radicals, is the rate-determining step in this reaction.

2-Sulfanylhydroquinone Dimer as a Switchable Fluorescent Dye.

A new dye was developed, the photoluminescence properties of which are controlled by a chemical reaction. The fluorescence properties of 2-sulfanylhydroquinone dimers depend on the number of hydroxyl groups that are acylated. Unprotected or monoacylated 2-sulfanylhydroquinone dimers displayed good fluorescence properties, whereas diacylated and tetraacylated 2-sulfanylhydroquinone dimers showed dramatically decreased fluorescence.

Development of a microwave-assisted sustainable conversion of furfural hydrazones to functionalised phthalimides in ionic liquids.

A sustainable synthetic procedure to convert furfural hydrazones into functionalised phthalimides was developed. The reaction was performed in a microwave using a hydrophilic ionic liquid, [bmim][Cl], as the solvent which could be readily recovered by a simple extraction. The ionic liquid was successfully recycled with no significant loss in product yields.

Thiol-Catalyzed Radical Decyanation of Aliphatic Nitriles with Sodium Borohydride.

Radical decyanation of aliphatic nitriles was achieved in the presence of NaBH and a thiol. The reaction proceeds via a radical mechanism involving borane radical anion addition to nitrile to form an iminyl radical, which undergoes carbon-carbon cleavage. Reductive radical addition to acrylonitrile is followed by decyanation to give a two-carbon homologated product in a net radical ethylation reaction.

Synthesis of α-Trifluoromethylated Ketones from Vinyl Triflates in the Absence of External Trifluoromethyl Sources.

A novel method for the conversion of vinyl triflates into α-trifluoromethylated ketones in the absence of external trifluoromethyl sources is described. This process accomplishes an efficient migration of the trifluoromethyl group of the triflate to the α-position in the ketone through a radical process. The reaction proceeds by the addition of a trifluoromethyl radical to the vinyl triflate and subsequent fragmentation of the trifluoromethane sulfonyl radical.

A regioselective double Stille coupling reaction of bicyclic stannolanes.

A regioselective double Stille coupling reaction was explored using bicyclic stannolanes that were easily prepared from the radical cascade reaction of β-amino-α-methylene esters. Various 1-bromo-2-iodoarenes underwent the double coupling reaction to afford benzoisoindole derivatives in a regioselective manner, where the carbon attached to the iodine selectively coupled with the vinylic carbon, and then the carbon attached to bromine coupled with the alkyl carbon. The combination of intra- and intermolecular coupling reactions provided hexahydroindeno[1,2-b]pyrrole derivatives in good yields.

Modulation of cellulase activity by charged lipid bilayers with different acyl chain properties for efficient hydrolysis of ionic liquid-pretreated cellulose.

The stability of cellulase activity in the presence of ionic liquids (ILs) is critical for the enzymatic hydrolysis of insoluble cellulose pretreated with ILs. In this work, cellulase was incorporated in the liposomes composed of negatively charged 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoglycerol (POPG) and zwitterionic phosphatidylcholines (PCs) with different length and degree of unsaturation of the acyl chains. The liposomal cellulase-catalyzed reaction was performed at 45°C in the acetate buffer solution (pH 4.

Asymmetric Synthesis of Bicyclic Nitrocyclopropanes from Primary Nitro Compounds and Stereoselective Formation of Tetrahydro-2H-cyclopenta[b]furans via Ring Expansion/Cyclization Reaction.

Optically active bicyclic nitrocyclopropanes are readily prepared from primary chiral nitro compounds, prepared by the conjugate addition of propionaldehyde to a nitro alkene in the presence of proline-derived organocatalysts. The one-step cyclopropanation took place smoothly in a highly stereoselective manner regardless of the stereogenic center adjacent to the allylic unit. Although the allylation reaction catalyzed by BF3·OEt2 provides a mixture of two possible diastereomers, subsequent oxidation of the alcoholic carbon after the formation of nitrocyclopropanes gave diastereomerically pure single products.

Rapid conversion of sorbitol to isosorbide in hydrophobic ionic liquids under microwave irradiation.

Sorbitol was effectively converted to isosorbide by treatment with [TMPA][NTf2 ] in the presence of catalytic amounts of TsOH under microwave heating at 180 °C. The reaction completed within 10 min and isosorbide was isolated to about 60%. Ionic liquids were readily recovered by an extraction treatment and reused several times.

Preparation of 2,3-dihydrofurans via a double allylic substitution reaction of allylic nitro compounds.

A one-step conversion of allylic nitro compounds to substituted 2,3-dihydrofurans has been developed. Allylic nitro compounds, which are readily available from nitroalkenes and formaldehyde, underwent a double allylic substitution reaction catalyzed by a palladium complex to give 2,3-dihydrofurans in good yield.

Gold(I)-catalyzed synthesis of optically active 1,4-oxazepan-7-ones.

Optically active seven-membered lactones, dimethyleneoxazepanones, were readily prepared in good yields from chiral β-(N-propargylic)amino-α-methylene carboxylic acid tert-butyl esters in the presence of catalytic amounts of Ph3PAuCl and Cu(OTf)2. A smooth 7-exo-dig cyclization was observed.

Efficient conversion of polyamides to ω-hydroxyalkanoic acids: a new method for chemical recycling of waste plastics.

An efficient transformation of polyamides to ω-hydroxy alkanoic acids was achieved. Treatment of nylon-12 with supercritical MeOH in the presence of glycolic acid gave methyl ω-hydroxydodecanoate in 85% yield and the alcohol/alkene selectivity in the product was enhanced to up to 9.5:1.

4,4'-Diarylsulfanyl-2,2',5,5'-tetraoxybiaryl derivatives as a water-soluble fluorescent dye.

4,4'-Disulfanyl-2,2',5,5'-tetrahydrobiaryl (5,5'-disulfanyl hydroquinone dimer) derivatives were readily synthesized from benzoquinone and thiols via an oxidative coupling reaction. The hydroquinone dimers showed strong fluorescence upon excitation at 330 nm, and it was observed that the presence of the sulfanyl groups at the C4 and C4' positions is important for achieving strong photoluminescence. The tetrapotassium salts of the hydroquinone dimers also showed good water solubility, but the fluorescence disappeared rapidly on dissolution in water.

Preparation of optically active bicyclodihydrosiloles by a radical cascade reaction.

Bicyclodihydrosiloles were readily prepared from optically active enyne compounds by a radical cascade reaction triggered by tris(trimethylsilyl)silane ((Me3Si)3SiH). The reaction was initiated by the addition of a silyl radical to an α,β-unsaturated ester, forming an α-carbonyl radical that underwent radical cyclization to a terminal alkyne unit. The resulting vinyl radical attacked the silicon atom in an SHi manner to give dihydrosilole.

A rapid route to aminocyclopropanes via carbamatoorganozinc carbenoids.

Easy as 1,2,3: Reaction of methyl carbamate, triethyl orthoformate, and readily available alkenes provides a highly practical preparation of protected aminocyclopropanes. The reaction proceeds with preferential cis addition to alkenes, and cleavage of the methyl carbamate gives the free aminocyclopropanes as their HI salts.

A radical cascade cyclization to prepare dihydrothiophenes induced by thiyl radicals as sulfur biradical equivalents.

Bicyclic dihydrothiophenes are readily prepared by a radical cascade cyclization reaction triggered by the addition of a thiyl radical under thermal or photoirradiation conditions. The translocated radical attacks the sulfur atom in the initial radical donor unit in an SHi manner. Sufficient stereoselectivity is achieved when a large excess of disulfide is used for the reaction under photoirradiation conditions.