N-(p-dodecylphenylsulfonyl)-2-pyrrolidinecarboxamide: a practical proline mimetic for facilitating enantioselective aldol reactions

A highly practical and readily available proline surrogate has been developed with improved solubility properties in common, nonpolar organic solvents. This sulfonamide-based catalyst has proven highly effective at facilitating enantioselective and diastereoselective aldol reactions with a range of substrates in nonpolar organic solvents in the presence of a single equivalent of water. Additionally, catalyst loading as low as 2 mol % can be employed in the absence of any organic solvent with continued high levels of selectivity.     

Pictet-Spengler condensation reactions catalyzed by a recyclable H+-montmorillonite as a heterogeneous Brønsted acid

Catalytic performance of different cation-exchanged montmorillonite clays has been investigated in the Pictet-Spengler C-C bond forming reaction. H⁺-Montmorillonite was found to be a very efficient and reusable catalyst for the endo cyclization of β-phenylethylamine derivatives with aldehydes under solvent-free conditions. In addition, an aqueous condensation version for the synthesis of tetrahydro-β-carbolines using the H⁺-montmorillonite catalyst has been developed. In these environmentally friendly processes, the use of organic solvents was avoided and the catalyst was recycled with maintenance of high catalytic activity.     

Enantioselective fluorescent recognition of a soluble "supported" chiral acid: toward a new method for chiral catalyst screening

The long-chain aliphatic-group-substituted mandelic acid 3c, which is soluble only in THF and insoluble in water and many polar/nonpolar organic solvents, has been synthesized. This unique solubility allows 3c to be easily isolated from reaction mixtures and makes it potentially useful for catalyst screening. The fluorescent sensors (R)- and (S)-1 can be used to determine the ees of various samples of 3c generated from a series of catalyst screening experiments. The fluorescence measurements correlate well with the conventional HPLC-chiral column analysis. This work demonstrates that the enantioselective fluorescent recognition of organic substrates can lead to a fundamentally new method for chiral catalyst screening. [reaction: see text]     

Development of a new triphase catalyst and its application to the epoxidation of allylic alcohols

[see reaction]. A new triphase catalyst has been developed. When an aqueous solution of H3PW12O40 (1) was added to a solution of the amphiphilic chain copolymer 2, a new self-assembled and macroporous complex 3 was formed. This complex was effective as a catalyst in the epoxidation of allylic alcohols. Even in the use of 2.7 x 10(-5) mole equiv of the catalyst, the epoxidation with aqueous H2O2 proceeded without organic solvents to give the corresponding epoxy alcohols in high yields.     

清洁催化氧化合成己二酸

以新颖的过氧钨酸盐——有机酸配位络合物为催化剂,在无溶剂和无相转移剂的条件下,用30％的过氧化氢氧化环己烯合成己二酸,其收率可达93－95％。本文讨论了配位体种类及催化剂用量对反应的影响。     

Brönsted acid hydrotrope combined catalyst for environmentally benign synthesis of quinoxalines and pyrido[2,3-b]pyrazines in aqueous medium

A new Brönsted acid hydrotrope combined catalyst (BAHC) has been developed and applied in acid catalyzed synthesis of pyrido[2,3-b]pyrazines and quinoxalines in an aqueous medium at ambient temperature with excellent yields. Interestingly, the catalyst can be easily recovered after the reactions and reused. Furthermore, BAHC catalyst worked well and avoids the use of organic solvents. We have reported herein the synthetic pathway which has less disastrous effect in the atmosphere and human survival.     

Organocatalytic direct michael reaction of ketones and aldehydes with beta-nitrostyrene in brine

We have developed a direct, asymmetric Michael reaction that can be performed in brine or seawater without addition of organic solvents. A bifunctional catalyst with long hydrophobic alkyl chains efficiently catalyzed Michael reactions and afforded the desired products in excellent yield with high enantiomeric excess, even when only an equal molar ratio of the donor to acceptor was used.     

Synthesis of triazolo indazolones using 3D mesoporous aluminosilicate catalyst with nanocage structure

Mesoporous Aluminosilicate (AlKIT-5) has been found to be an efficient catalyst for one-pot synthesis of triazolo[1,2-a]indazole-1,3,8-trione derivatives from dimedone, urazole, and aromatic aldehydes using acetonitrile as a solvent. This new method is simple, effective, ecofriendly, and consistently has the advantage of excellent yields (80-96%) and short reaction time (30-60 min). The effect of the catalyst weight, aluminum content in the catalyst, and the solvents on the synthesis of triazolo[1,2-a]indazole-1,3,8-trione derivatives has been investigated. It has been found that the catalyst can be recycled for several times without much affecting its activity for a variety of organic transformations.     

An amine sulfonamide organocatalyst for promoting direct, highly enantioselective α-aminoxylation reactions of aldehydes and ketones

A novel, pyrrolidine sulfonamide-based organocatalyst has been developed and used to catalyze direct, efficient and α-aminoxylation reactions of aldehydes and ketones with excellent regio- and enantioselectivities. Unlike l-proline, the new catalyst exhibits high activity and enantioselectivity when used in a variety of organic solvents.     

Mohr's Salt Hexahydrate: A Novel,Cheap and Powerful Reagent for Green Synthesis of Biscoumarins on Water

A new and convenient method for the synthesis of biscoumarins based on the condensation of 4‐hydroxycoumarin and aromatic aldehydes in the presence of Mohr's salt hexahydrate (ferrous ammonium sulfate hexahydrate) as a novel catalyst on water is developed. This method has advantages such as the use of inexpensive and available reagent, avoidance of organic solvents, short reaction times, and high product yields.     

Significant rate acceleration of the aza-Michael reaction in water

The addition of amines to conjugated alkenes has been carried out in water at room temperature very efficiently without any catalyst. Significant rate acceleration of this reaction is observed in water compared to organic solvents.     

Cu(II) 2-quinoxalinol salen catalyzed oxidation of propargylic,benzylic, and allylic alcohols using tert-butyl hydroperoxide in aqueous solutions

The synthesis of carbonyl compounds by oxidation of alcohols is a key reaction in organic synthesis. Such oxidations are typically conducted using catalysts featuring toxic metals and hazardous organic solvents. Considering green and sustainable chemistry, a copper(II) complex of sulfonated 2-quinoxalinol salen (sulfosalqu) has been characterized as an efficient catalyst for the selective oxidation of propargylic, benzylic, and allylic alcohols to the corresponding carbonyl compounds in water when in combination with the oxidant tert-butyl hydroperoxide. The reactions proceed under mild conditions (70 °C in water) to produce yields up to 99% with only 1 mol % of catalyst loading. This reaction constitutes of a rare example of propargylic alcohol oxidation in water, and it makes this process greener by eliminating the use of hazardous organic solvents. Excellent selectivity was achieved with this catalytic protocol for the oxidation of propargylic, benzylic, and allylic alcohols over aliphatic alcohols. The alcohol oxidation is thought to go through a radical pathway.     

Molecular sieves: an efficient and reusable catalyst for multi-component synthesis of dihydropyrano[2,3-C]pyrazole derivatives

An efficient synthesis of dihydropyrano[2,3-C]pyrazole derivatives catalyzed by molecular sieves in ethanol under reflux and ultrasound irradiation has been described. The efficiency of catalyst has been compared with other aluminates and silicate based catalyst in order to optimize catalyst for the said organic transformation. This protocol is very useful due to easy recovery of the catalyst and its reusability, short reaction time, excellent yields, and avoidance of environmentally hazardous solvents.     

高效可回收催化剂In(OTf)_3用于无溶剂条件下Pechmann缩合反应(英文)

In(OTf)3 plays the role of a Lewis acid catalyst in the Pechmann condensation of phenols with β-ketoesters under solvent-free conditions to give coumarin derivatives. This novel and inexpensive method has advantages such as short reaction time, excellent product yields, and avoids the use of organic solvents in agreement with green chemistry principles. Catalyst loadings can be as low as 1 mol% to give high yields of the corresponding coumarins at 80 °C. The catalyst can be recovered after the reaction, and reused with only a slight decrease in the yield.     

Rh-TPPTS/CTAB-MMT催化剂的制备及其催化长链烯烃氢甲酰化反应性能研究

通过浸渍法将水溶性铑膦配合物(Rh-TPPTS)负载到由十六烷基三甲基溴化铵(CTAB)修饰的蒙脱土(MMT)上,制备出Rh-TPPTS/CTAB-MMT负载型催化剂.采用XRD,FTIR,TG,BET,31P CP-MAS NMR和分散性实验对催化剂进行了表征.结果表明:水溶性铑膦配合物成功地负载到有机MMT上,并且该催化剂在有机溶剂中具有很好的分散性.该催化剂对于1-癸烯的氢甲酰化反应具有好的催化活性.在100℃、4 MPa、甲苯为溶剂的条件下,催化1-癸烯氢甲酰化可获得93.0%的转化率,95.8%的醛的选择性,2.1的正异比,137 h-1的TOF值.并对不同链长烯烃底物进行了考察.随着烯烃碳链的增加,醛的选择性下降,但是正异比有所增加.     

Nickel‐Catalyzed Cross‐Electrophile Coupling with Organic Reductants in Non‐Amide Solvents

Cross‐electrophile coupling of aryl halides with alkyl halides has thus far been primarily conducted with stoichiometric metallic reductants in amide solvents. This report demonstrates that the use of tetrakis(dimethylamino)ethylene (TDAE) as an organic reductant enables the use of non‐amide solvents, such as acetonitrile or propylene oxide, for the coupling of benzyl chlorides and alkyl iodides with aryl halides. Furthermore, these conditions work for several electron‐poor heterocycles that are easily reduced by manganese. Finally, we demonstrate that TDAE addition can be used as a control element to ‘hold’ a reaction without diminishing yield or catalyst activity.     

Ultrasound-assisted synthesis of diversely functionalized tetrahydro-1H-Indole-4(5H)-one using Brønsted base silica sodium carbonate (SSC) as a catalyst under solvent-free conditions

An ultrasound-promoted, environmentally benign, efficient procedure has been developed for the synthesis of biologically active tetrahydro-1H-indol-4(5H)-one using heterogeneous Brønsted base silica sodium carbonate (SSC) as a catalyst under solvent-free conditions. In comparison to the conventional methods, this efficient green protocol provides remarkable advantages such as good to excellent yields, shorter reaction time, low cost, and easy workup procedure and bypasses the use of hazardous transition-metal catalysts and organic solvents.     

A green and convenient protocol for the synthesis of diarylmethanes via a one-pot,three-component reaction catalyzed by a novel silica tungstic acid (STA) under solvent-free conditions

A cost-effective and eco-friendly synthesis of diarylmethanes derivatives has been developed through the Mannich type Friedel–Crafts addition reaction of tertiary aromatic amine formaldehydes with β-naphthol/indole using silica-supported tungstic acid (STA) as a recyclable heterogeneous acid catalyst in solvent-free condition. Here, we proposed two schemes using the same catalyst. The effects of different solvents have been studied and a comparison of silica-supported tungstic acid with different acid catalysts has also been made.     

Chemical Fixation of CO2 with Highly Efficient ZnCl/[BMIm]Br Catalyst System

The search for environmentally benign and economic process has been the impetus for much of the research involving epoxide and carbon dioxide coupling in view of the so called "green chemistry" and" atom economy ", since CO2 is a renewable resource and can be used as a safe and cheap C 1 building block to synthesize useful organic compounds without producing any coproducts.[1-2] One of the most attractive synthetic goals starting from carbon dioxide is the chemical fixation of CO2 onto epoxide to afford the five-membered cyclic carbonates (Scheme 1),which are excellent aprotic polar solvents and are used extensively as intermediates in the production of pharmaceuticals and fine chemicals.[3] In the last decades of the twentieth century numerous catalytic systems have been developed for this transformation. While some advances have been obtained, all suffer from either low catalyst stability/reactivity, the need for co-solvent, or the requirement for high pressure and/or catalyst costing expensive.[4] Therefore, to find an effective,not exrensive, environmentally benign and economic catalyst system is urgent.In this paper, chemical fixation of CO2 with mono-substituted terminal epoxides or cyclohexene oxide to form cyclic carbonates under the ZnCl2/[BMIm]Br Catalyst System without using additional organic solvents was achieved in excellent selectivity (＞98%) and TOF(5410h-1) Besides,the pure cis-cyclic carbonate of cyclohexene oxide was obtained in this catalyst system.It was important to note that the catalyst could be recovered by simple vacuum distillation of the corresponding cyclic carbonates and could be used six times almost without losing its catalytic activity and selectivity. The catalyst system was found to be applicable to a variety of terminal epoxides and cyclohexene oxide, forming the corresponding cyclic carbonates in very high TOF and more than 98% selectivity. Based on the obtained results, we also propose the plausible mechanism for this chemical fixation reaction of CO2.     

Controlled/“Living” Radical Polymerization Applied to Water‐Borne Systems

Atom transfer radical polymerization (ATRP), a controlled/“living” radical polymerization, has been extended to water‐borne polymerization systems. In order to obtain a controlled ATRP reaction in a water‐borne system, various criteria must be met, which are not necessary when conducted in organic solvents. The effect of surfactant, monomer, catalyst and initiator employed will be discussed, as each had a profound effect on the success of the ATRP reaction.