Solvent‐free cyanosilylation of aldehydes catalyzed by SmI2

A novel method to obtain racemic cyanohydrin silylethers by reaction of trimethylsilyl cyanide with a variety of aldehydes promoted by catalysis of SmI₂ is reported. The corresponding cyanosilylethers were obtained in high yields (up to 99%) in solvent‐ free conditions at room temperature within a relatively short time using 0.01–0.5 mol% catalyst loadings. Copyright © 2007 John Wiley & Sons, Ltd.     

Metal and solvent‐free cyanosilylation of carbonyl compounds with tris(pentafluorophenyl)borane

A highly effective method of the cynaosilylation of aldehydes and ketones with TMSCN in the presence of catalytic amount of B(C₆F₅)₃ [tris(pentafluorophenyl)borane] has been developed. Cyano transfer from TMSCN to carbonyl group proceeds at room temperature under solvent‐free conditions. Various alehydes and ketones have been converted into the corresponding trimethylsilylether within short reaction times with excellent yield under mild conditions. Copyright © 2008 John Wiley & Sons, Ltd.     

Enantioselective cyanosilylation of ketones by a catalytic double-activation method with an aluminium complex and an N-oxide

Double-activation catalysis promises high catalytic efficiency in the enantioselective cyanosilylation of ketones through the combined use of a Lewis acid and a Lewis base. Catalyst systems composed of a chiral salen-Al complex and an N-oxide have high catalytic turnovers (200 for aromatic ketones, 1000 for aliphatic ones). With these catalysts, a wide range of aliphatic and aromatic ketones were converted under mild conditions into tertiary cyanohydrin O-TMS ethers in excellent yields and with high enantioselectivities (94% ee for aromatic ketones, 90% ee for aliphatic ones). Preliminary mechanistic studies revealed that the salen-Al complex played the role of a Lewis acid to activate the ketone and the N-oxide that of a Lewis base to activate TMSCN; that is, double activation.     

Solvent‐free synthesis of rotaxanes

Rotaxane‐type (macro)molecules are important materials in various fields of research, with many approaches for their synthesis having been developed over the past 30 years or so. When prepared in solution, the efficiency of interlocking pseudorotaxane complexes into the corresponding rotaxanes relies, to a great extent, on the affinity between the host and guest components; these interactions are not always sufficiently strong to overcome the deleterious effects of high reaction temperatures, competitive solvents, and low concentrations. Upon evaporating the solvent, however, the concentrations of the host and guest species increase significantly and, ultimately, their corresponding pseudorotaxanes can be generated with high efficiency in the solvent‐free residue. Furthermore, in the absence of the solvent, the influence of any disrupting byproducts (generated during the interlocking process) on the complexation equilibrium can also be largely reduced. Therefore, high synthetic efficiency and low consumption of solvents and energy can be expected when synthesizing rotaxanes under solvent‐free conditions. This mini‐review covers the main publications dealing with the solvent‐free syntheses of rotaxanes – those in which the interlocking step involves no solvent (or only a trace of it).     

Gallium(III) Iodide‐catalyzed Biginelli‐type Reaction Under Solvent‐free Conditions: Efficient Synthesis of Dihydropyrimidine‐2(1H)‐one Derivatives

The Biginelli‐type condensation of ethyl acetoacetate/cycloketone, aldehyde and urea/thiourea under solvent‐free condition catalyzed by 10% gallium(III) iodide to form dihydropyrimidine‐2(1H)‐one derivatives was described. This process offered one way to constructing dihydropyrimidine‐2(1H)‐ones in good to excellent yields with simple procedure and short reaction time.     

Ligand‐ and solvent‐free synthesis of 2‐aminobenzothiazoles by copper‐catalyzed tandem reaction of 2‐haloanilines with isothiocyanates

We report an environmentally friendly, efficient and practical method for the synthesis of 2‐aminobenzothiazoles by a copper(II)‐catalyzed tandem reaction of 2‐haloanilines with isothiocyanates under ligand‐ and solvent‐free conditions in air. The developed methodology conforms to the principles of 'green chemistry' and addresses the shortage of such methods for the synthesis of 2‐aminobenzothiazoles. The reaction is quite general and generates a variety of 2‐aminobenzothiazoles in good to excellent yields. Copyright © 2012 John Wiley & Sons, Ltd.     

Solvent‐free synthesis of propargylamines catalyzed by an efficient recyclable ZnO‐supported CuO/Al2O3 nanocatalyst

An efficient nanocatalyst of ZnO‐supported CuO/Al₂O₃ (CuO/ZnO/Al₂O₃ nanocatalyst) was prepared by the co‐precipitation method and characterized by scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, X‐ray powder diffraction and Brunauer–Emmett–Teller surface area analysis. CuO/ZnO/Al₂O₃ nanocatalyst proved to be a very efficient catalyst on the synthesis of propargylamines under solvent‐free conditions in high yields. Moreover, the catalyst can be recyclable without reducing catalytic activity up to five times.     

Cyanosilylation of carbonyl compounds catalyzed by sodium L‐histidine

An efficient protocol for the addition of trimethyl silanecarbonitrile to carbonyl compounds by employing 1 mol% of L ‐histidine sodium salt alone as the catalyst is presented. A variety of aromatic, aliphatic and cyclic carbonyl compounds have been converted into the corresponding trimethylethers in excellent yield (up to 99%) under mild conditions. Copyright © 2007 John Wiley & Sons, Ltd.     

L-Proline Catalyzed Enamination of β-Dicarbonyl Compounds under Solvent-free Conditions

A simple, general and efficient method has been developed for synthesis of various β-enamino ketones and esters by reacting β-dicarbonyl compounds with amines using a catalytic amount of L-proline at room temperature under solvent-free conditions in excellent yields.     

Highly enantioselective cyanosilylation of ketones catalyzed by a bifunctional Ti(IV) complex

A bifunctional catalyst system composed of (S)-prolinamide (2a), titanium(IV) isopropoxide, and phenolic N-oxide (3f) exhibited high catalytic efficiency in the enantioselective cyanosilylation of ketones. In the presence of 2.5 mol % catalyst, a variety of aromatic and aliphatic ketones were converted into the corresponding tertiary cyanohydrin O-TMS ethers in excellent yields (up to 96%) and high enantioselectivities (up to 96% ee). A proposed catalytic cycle was illustrated to explain the origin of the asymmetric induction.     

Solvent‐free synthesis of α‐aminonitriles from aldehydes,amines and trimethylsilyl cyanide catalyzed by thallium(III) chloride tetrahydrate

A straightforward and efficient method has been developed for the synthesis of α‐aminonitriles by combining aldehydes, amines and trimethylsilyl cyanide in the presence of a catalytic amount of thallium(III) chloride tetrahydrate (1 mol%) under solvent‐free conditions at room temperature. Copyright © 2008 John Wiley & Sons, Ltd.     

Selective hydrosilylation of ketones catalyzed by in situ‐generated iron NHC complexes

Aryl alkyl‐, heteroaryl alkyl‐ and dialkyl ketones were readily reduced to their corresponding secondary alcohols in high yields, using the commercially available and inexpensive polymeric silane polymethylhydrosiloxane (PMHS), as reducing agent. The reaction is catalyzed by an in situ ‐generated iron complex, conveniently generated from iron(II) acetate and the commercially available N‐heterocyclic carbene (NHC) precursor IPr·HCl. Copyright © 2011 John Wiley & Sons, Ltd.     

氮氧双功能salen催化剂在酮的不对称硅氰化反应中的应用

通过在催化剂的不同位置同时引入LALB（Lewis acid/Lewis base）双功能基团（包括氮氧偶极基团和金属钛中心）来改善其催化活性和立体控制能力,合成基于salen骨架结构的新型氮氧双功能催化剂.在相对温和的条件下成功的将该类双功能催化剂应用于酮的不对称硅氰化反应,表现出了中等程度的选择性和非常高的反应活性...     

Solvent‐free Liquid Crystals and Liquids from DNA

As DNA exhibits persistent structures with dimensions that exceed the range of their intermolecular forces, solid‐state DNA undergoes thermal degradation at elevated temperatures. Therefore, the realization of solvent‐free DNA fluids, including liquid crystals and liquids, still remains a significant challenge. To address this intriguing issue, we demonstrate that combining DNA with suitable cationic surfactants, followed by dehydration, can be a simple generic scheme for producing these solvent‐free DNA fluid systems. In the anhydrous smectic liquid crystalline phase, DNA sublayers are intercalated between aliphatic hydrocarbon sublayers. The lengths of the DNA and surfactant are found to be extremely important in tuning the physical properties of the fluids. Stable liquid‐crystalline and liquid phases are obtained in the ?20 °C to 200 °C temperature range without thermal degradation of the DNA. Thus, a new type of DNA‐based soft biomaterial has been achieved, which will promote the study and application of DNA in a much broader context.     

无溶剂条件下碘催化合成三吲哚甲烷的研究

室温无溶剂条件下,碘(5 mol%)催化吲哚与原甲酸三乙酯的反应,生成相应的三吲哚甲烷,产率适中到较好且无副产物。     

Molecular Iodine Catalyzed One‐pot Aza‐Diels‐Alder Reaction under Solvent‐free Conditions

Catalyzed by molecular iodine at room temperature, under solvent‐free conditions, a two component aza‐Diels‐Alder cyclization of N‐vinyl‐2‐pyrrolidinone with N‐arylimine gave tetrahydroquinoline derivatives in good yields and high stereo‐selectivity. And three components aza‐Diels‐Alder reaction of N‐vinyl‐2‐pyrrolidinone, anilines and indole‐3‐carbaldehydes under the same condition afford only cis‐product in good yields.     

Solvent‐free ring‐opening polymerization of lactones with hydrogen‐bonding bisurea catalyst

Development of effective organocatalysts for the living ring‐opening polymerization (ROP) of lactones is highly desired for the preparation of biocompatible and biodegradable polyesters with controlled microstructures and physical properties. Herein, a new class of hydrogen‐bond donating bisurea catalysts is reported for the ROP of lactones under solvent‐free conditions. ROP of lactones mediated by the bisurea/7‐methyl‐1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (MTBD) catalyst exhibits a living/controlled manner, affording the polymers and copolymers with the well‐defined structure, predictable molecular weight, narrow molecular weight distribution, and high selectivity for monomer at low catalyst loadings at ambient temperature. The possible mechanism of bisurea/MTBD‐catalyzed ROP of lactones is proposed, in which the bisurea activates the carbonyl group of lactones while MTBD facilitates the nucleophilic attack of the initiating/propagating alcohol by hydrogen bonding. Moreover, the poly(ε‐caprolactone‐co‐δ‐valerolactone) [P(CL‐co‐VL)] random copolymers with various compositions were synthesized using the bisurea/MTBD catalyst. The measurements of thermal properties and crystalline structure demonstrate that the CL and VL units are cocrystallized in the crystalline phase of P(CL‐co‐VL) copolymers. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 90–100     

Solvent‐free fabrication of proton‐conducting membranes based on commercial elastomers

Five different types of elastomers were examined as the matrix materials in the preparation of non‐fluorinated proton exchange membranes utilizing a solvent‐free route via the in situ reaction of sodium 4‐styrenesulfonate (NaSS). The morphology of the elastomer/NaSS vulcanizates was studied to evaluate the effect of polarity, viscosity and saturation degree of the elastomer matrixes. Much better dispersion of NaSS was found in chlorosulfonated polyethylene rubber (CSM) and hydrogenated nitrile butadiene rubber (HNBR) matrixes than in the other three types of elastomer matrixes. For CSM/NaSS and HNBR/NaSS proton exchange membranes, distinctive membrane properties were observed and correlated with their different structure and morphologies. The CSM/NaSS membranes exhibited the proton conductivity as high as ~0.03 S cm^?1 and the selectivity (the ratio of proton conductivity to methanol permeability) higher than that of Nafion. Copyright © 2015 John Wiley & Sons, Ltd.     

Solvent‐free Chemoselective Synthesis of 1,1‐diacetates Catalyzed by Iron Zirconium Phosphate

In the present study, a mild, rapid, and efficient method for the protection of aldehydes with acetic anhydride (AA) in the presence of iron zirconium phosphate (ZPFe), at room temperature is reported. Selective conversion of aldehydes was observed in the presence of ketones. Under these conditions, different aldehydes bearing electron‐withdrawing and electron‐donating substituents were reacted with AA and the corresponding 1,1‐diacetates (acylals) were obtained in high to excellent yields. The steric and electronic properties of the different substrates had a significant influence on the reaction conditions. Also, the deprotection of 1,1‐diacetates has been achieved using this catalyst in water. The catalyst was characterized by several physico‐chemical techniques. It was recovered easily from the reaction mixture, regenerated, and reused at least 7 times without significant loss in catalytic activity. This protocol has the advantages of easy availability, stability, reusability of the eco‐friendly catalyst, chemoselectivity, simple experimental and work‐up procedure, solvent‐free conditions and only a stoichiometric amount of AA is needed.