Highly Efficient AILs/L‐Proline Synergistic Catalyzed Three‐Component Asymmetric Mannich Reaction

A three‐component asymmetric Mannich reaction of isovaleraldehyde, methyl ketones, and aromatic amines was efficiently synergistic catalyzed by amide‐task‐specific ionic liquids (AILs)/L‐proline under mild conditions. The corresponding asymmetric Mannich reaction adducts were obtained in moderate to high yields and stereo selectivity in all the cases tested. The product was easily isolated, and the remaining catalysis system can be readily recovered and reused at least three times without significant loss of catalytic activity and selectivity.     

DpenPhos/Rh（Ⅰ） Catalyzed Asymmetric Hydrogenation of Dehydro- β -Amino Acid Esters

本文研究了一类结构可调手性单齿亚磷酰胺配体DpenPhos在Rh（I）催化的E和Z型β-脱氢氨基酸酯的不对称催化氢化反应中的应用.经过系统的反应条件和配体结构优化,发现N原子上含有H的亚磷酰胺配体与Rh（I）形成的催化剂通常比N原子上不含H的配体表现出更高的反应活性.在E型β-脱氢氨基酸酯的不对称氢化反应中,催化剂（R,R）-3k/Rh（I）表现突出,可以实现底物的常压催化氢化,取得了92%～96%的对映选择性,催化剂用量可降低至0.2 mol%;对于Z型β-脱氢氨基酸酯的不对称氢化反应,则（R,R）-3l/Rh（I）为最优催化剂,可以获得92%～98%ee值的氢化产物,特别是对于β-芳基取代衍生物的氢化反应,相应氢化产物的ee值可以达到96%～98%.该类催化剂为天然或非天然光学活性β氨基酸的合成提供了一个简便、高效的方法.     

Cu/Pd Synergistic Dual Catalysis: Asymmetric α-Allylation of an α-CF3 Amide

Despite the burgeoning demand for fluorine-containing chemical entities, the construction of CF₃-containing stereogenic centers has remained elusive. Herein, we report the strategic merger of Cu^I/base-catalyzed enolization of an α-CF₃ amide and Pd⁰-catalyzed allylic alkylation in an enantioselective manner to deliver chiral building blocks bearing a stereogenic carbon center connected to a CF₃, an amide carbonyl, and a manipulable allylic group. The phosphine complexes of Cu^I and Pd⁰ engage in distinct catalytic roles without ligand scrambling to render the dual catalysis operative to achieve asymmetric α-allylation of the amide. The stereoselective cyclization of the obtained α-CF₃-γ,δ-unsaturated amides to give tetrahydropyran and γ-lactone-fused cyclopropane skeletons highlights the synthetic utility of the present catalytic method as a new entry to non-racemic CF₃-containing compounds.     

Substitution Reactions by Azide and Thiocyanide Anions in Room Temperature Ionic Liquids

Conducted in the ionic liquids,activated and inactivated halides,acyl chlorides,tosylate and bezotriazolyl acylates were converted to corresponding azide and thiocyanide compounds in high yields under mild conditions.     

Organic Reactions in Ionic Liquids： Ionic Liquid-promoted Three-component Condensation of Benzotriazole with Aldehyde and Alcohol

1-(α-Alkoxyalkyl)benzotriazoles are readily synthesized from three-component condensation of benzotriazole with aldehyde and alcohol in ionic liquid [Bmim]PF6.     

BrØnsted Reusable Acidic Ionic Liquids Catalyzed Biginelli Reaction under Solvent-Free Conditions

Abstract

2-Pyrrolidonium hydrogensulfate, N-methyl-2-pyrrolidonium hydrogensulfate, and N-methyl-2-pyrrolidonium dihydrogenphosphate as Brønsted reusable acidic ionic liquids (ILs) catalyzed the preparation of 3,4-dihydropyrimidin-2(1H)-one (thione) derivatives from ethyl/methyl acetoacetate, urea/thiourea, and aromatic aldehydes under thermal solvent-free conditions.     

D,L‐α‐Tocopherol Synthesis Catalyzed by the Brønsted Acidic Ionic Liquids

Abstract

The synthesis of D,L‐α‐tocopherol from trimethylhydroquinone and isophytol using the Brønsted acidic SO₃H‐functionalized ionic liquids as catalysts was explored. The catalytic activities of the SO₃H‐functionalized ionic liquids were dependent on their anions. The yield of D,L‐α‐tocopherol also depended on the solvent, which was the reaction medium. A yield of 94.3% was obtained using the SO₃H‐functionalized ionic liquid with [BF₄ ^?] anion as catalyst in propylene carbonate/heptane. The reaction mixture exhibited good biphasic behaviors, so that the produced D,L‐α‐tocopherol could be separated by decantation. The SO₃H‐functionalized ionic liquids could be reused after the removal of water.     

Recent Advances in Organic Reactions Catalyzed by Lanthanide（Ⅲ） Complexes

Lanthanide compounds have been attracting much attention in organic synthesis.Chiral Ln-substituted BINOL have been widely studied in several asymmetric organic reactions.LnCl3 and Ln(OTf)3 have been expected to serve as Lewis acide and have been applied to many important synthetic reactions in a one-pot manner,Ln(O-i-Pr)3 exhibits some basic characters,which also can be utilized in some special organic transformation.This article deals with some lanthanides(Ⅲ）complexes promoted organic reactios,which we have recently developed.     

Guanidinium Iodides-based Ionic Liquids： Synthesis and Application for Dye-sensitized Solar Cells（DSSCs）

A series of guanidinium ionic liquids(GILs) was designed, synthesized, and used as electrolytes for dye-sensitized solar celIs(DSSCs). The effect of electrolytes containing GILs on the photovoltaic performance of DSSCs was investigated. It is demonstrated that these GILs are promising for being used as electrolytes for DSSCs and a conversion efficiency of 4.1% can be obtained under AM 1.5 sun light irradiation.     

Asymmetric Allyltributylstannane Addition to Ketones Catalyzed by Chiral Indium（Ⅲ）-PYBOX Complex

An indium complex of chiral pyridine bis(oxazoline)(PYBOX)has been applied to the catalytic asymmetricallylation of ketones.It has been found that this chiral indium complex is strong enough to promote the reaction ofketones with allyltributylstannane smoothly.The products were obtained in moderate yields with low to moderateenantioselectivities.     

离子液体中的酶催化反应

离子液体作为酶催化反应的介质正越来越多的受到关注,因为与传统有机溶剂和水相比,酶在离子液体中表现出了更好的活性、热稳定性、立体选择性、对映体选择性和可循环性。本文综述了近几年来脂肪酶、氧化还原酶、蛋白酶在离子液体中的催化反应。     

Aromatic Compounds Mannich Reaction Using Economical Acidic Ionic Liquids Based on Morpholinium Salts as Dual Solvent-Catalysts

Economical acidic ionic liquids containing an alkanesulfonic acid group in a morpholinium cation were found to be effective catalysts for the Mannich reactions of various kinds of aromatic aldehydes, acetophenone and aromatic amines at mild reaction conditions. The satisfactory results were obtained with short reaction time, good yields of the Mannich bases and simplicity in the experimental procedure. These ionic liquids could be recycled and reused for up to five times without considerable decreasing in the catalytic activity.     

离子液体中的不对称合成研究进展

离子液体作为溶剂已广泛应用于许多有机化学反应.总结了离子液体中的不对称有机反应,如氢化反应、酰基化反应、环氧化反应、酶催化反应等.     

离子液体在不对称催化反应中的应用进展

综述了近年来离子液体在不对称催化反应中的应用,包括不对称Aldol反应、不对称氟化反应、酶催化的不对称还原反应、不对称催化氢化反应、不对称硅腈化反应、不对称环丙烷化反应、烯丙基的不对称取代反应、环氧化物的不对称开环反应、不对称环氧化反应、烯烃的不对称双羟基化反应、酶催化的醇的动力学拆分。参考文献43篇。     

离子液体中制备无机材料

离子液体作为潜在的“绿色”溶剂,具有许多传统溶剂无法比拟的优异性能,在有机合成、催化、液液分离和萃取等领域引起了广泛的研究。而在离子液体领域无机材料的制备是一个较新的发展分支,现已利用其合成出多种具有独特结构和性能的无机材料。本文就离子液体在无机材料制备方面的应用及发展趋势进行了综述。目前,对于制备无机材料,离子液体主要是作为电解液、表面活性剂或溶剂,本文介绍了其在应用中的优缺点,并指出该领域未来的发展趋势是离子热合成和集模板-溶剂-反应物于一身的离子液体反应。     

anti-Selective direct asymmetric Mannich reactions catalyzed by chiral pyrrolidine-based amino sulfonamides

The novel pyrrolidine-based amino sulfonamides (R,R)-2, (S)-3, and (S)-4 were designed and synthesized as organocatalysts and successfully applied for the anti-selective direct asymmetric Mannich reaction.     

Squaramide‐Catalyzed Asymmetric Reactions

Bifunctional squaramides have emerged as powerful hydrogen‐bonding catalysts for promoting a wide array of useful asymmetric reactions, which provides convenient methods for the construction of complex molecular structures and chiral biologically active compounds. This review highlights the recent advances of our research group in the chiral squaramide‐catalyzed asymmetric reactions, including Michael addition, Mannich reaction, aza‐Henry reaction, Strecker reaction as well as cascade or sequential reactions.     

氯铝酸室温离子液体中缩醛和缩酮反应

以取代硫酸等无机酸，实现清洁合成为目的，在1－烷基吡啶和1－甲基－3－ 烷基咪唑季胺盐与无水AlCl_3构成的室温离子液体为催化剂和反应介质中，尝试了 醛和酮与甲醇的缩合反应。醛与甲醇反应，产物以缩醛为主，酮与甲醇反应则有相 当量的Aldol缩合产物。依反应底物不同，可获得中至高的转化率和选择性。同时 ，一些产物因不溶于离子液体中而分层，便于产物分离。