Chiral pyrrolidine-azole conjugates: Simple and efficient asymmetric organocatalysts for Michael addition to nitrostyrenes

Simple pyrrolidine-azole conjugates have been synthesized and found to be efficient catalysts for asymmetric Michael addition to nitrostyrenes. The identified optimal catalysts, pyrrolidine-azoles 2, 8 and 13, could catalyze the asymmetric Michael addition of a range of Michael donors and nitrostyrenes in high yields (up to 99%) and excellent stereoselectivities (up to 99:1 dr and 97% ee).     

Synthesis of Chiral Sulfoxides and Application in Enantioselective Allylation of Aldehydes with Allyltrichlorosilane

1 Results The enantioselective addition of allylic organometallic reagents to aldehydes is a fundamental tool in organic synthesis.The high degree of both diastereo-and enantioselectivity gives the possibility to obtain a wide series of homoallylic alcohols,versatile intermediates in a great number of synthesis[1]. One of the most successful approaches is related to the discovery that organocatalytic activation of the nucleophilic allyltrichlorosilanes by means of neutral Lewis bases,such as formamides,...     

Recent Advances in the Development of Polymer-supported Phosphines

1 Introduction Recent years have seen a growing use of polymer-supported reagents by organic chemists in traditional solution-phase synthesis.Of the many reagents supported by polymers available, variations of triphenylphosphine are among the most broadly used. This is because triphenylphosphine is not only a reagent in a wide range of organic reactions~([1]), but it also serves as a ligand in many organometallic reagents~([2]).Most importantly, polymer-supported triphenylphosphine affords the…     

新型表面活性剂类硫脲高效催化硝基烯烃的不对称Michael加成(英文)

由N-BOC-胺甲基吡咯烷和异硫氰酸盐反应合成了一种新型结构的硫脲分子,将该具有表面活性剂类型的硫脲分子用作有机催化剂来催化硝基烯烃的不对称Michael加成,条件实验探索结果表明,最优的实验条件是,10 mol%催化剂,10 mol%的苯甲酸作为添加剂,用水做溶剂以及在室温反应温度.在该最优条件下,可以非常顺利地实现各种硝基烯烃与各类醛和酮的Michael加成,得到较高的收率(76%~97%),良好的几何选择性(顺∶反=82∶18~99∶1)以及对映选择性(ee值达到97%).     

Recent Advances in Catalytic Asymmetric Synthesis

The rapid development in the genomics and proteomics research has brought about an unprecedented number of potential new drug targets, which translates into an ever-increasing need to rapidly assemble highly pure small molecules （MRS850） with an increased structural complexity ＇to identify a small molecule partner for every gene product＇. Simultaneously, our increasing awareness of environmental aspects of synthesis places a nearly orthogonal set of requirements for the kinds of syntheses admissible in the future which can be expressed as a rule of 6S＇ s： selectivity and speed of the syntheses;     

Asymmetric epoxidation of <Emphasis Type="Italic">α</Emphasis>,<Emphasis Type="Italic">β</Emphasis>-unsaturated ketones using <Emphasis Type="Italic">α</Emphasis>,<Emphasis Type="Italic">α</Emphasis>-diarylprolinols as catalysts

Asymmetric epoxidation of α,β-unsaturated ketones has been extensively studied and several important procedures have been developed in the last decade. This review addresses the most significant advances in asymmetric epoxidation of α,β-unsaturated ketones using proline-derived α,α-diarylprolinols as catalysts. Special attention has been paid to the enantioselective epoxidation of chalcones, α,β-unsaturated trifluoromethyl, trichloromethyl ketones and β,γ-unsaturated α-keto esters based on the reseach of our group.     

Combined use of an alkene and a phosphine as a nucleophilic catalyst system for the cyanosilylation of carbonyl compounds

The catalytic potential of carbon nucleophiles has seldom been disclosed due to their reactivity toward carbon electrophiles to form stable carbon-carbon bonds, which are too strong to be cleaved for the expected catalytic cycles. We have developed an efficient catalytic cyanosilylation of carbonyl compounds with an in situ generated alkene/phosphine adduct, which is tuned not to couple with a carbonyl compound or an electron-deficient alkene under the reaction conditions when its nucleophilicity is translated into catalytic activity. In the presence of 3 mol% of methyl acrylate and 3 mol% of triphenylphosphine, a broad range of alkyl, alkenyl, and aryl ketones and aldehydes undergo cyanosilylation reaction with trimethylsilyl cyanide at room temperature to yield structurally diversified cyanohydrin silyl ethers in excellent yields. By using methyl acrylate/triphenylphosphine as a highly effective nucleophilic catalyst system for the cyanosilylation of carbonyl compounds, this study demonstrates a new concept for the development of useful organocatalysis utilizing the nucleophilicity of alkene/phosphine adducts generated in situ.     

H_8-NOBIN-脯氨酰胺有机催化不对称直接Aldol反应

以光活性H8-NOBIN和N-叔丁氧羰基-L-脯氨酸为原料合成了2个脯氨酰胺。该脯氨酰胺与三氟乙酸组合可有效催化芳香醛和酮的不对称直接Aldol反应．催化芳香醛和丙酮的反应化学产率最高达76％,对映体过量值达83％;催化对硝基苯甲醛和环己酮的反应化学产率高达98％,非对映选择性达88：12,反式异构体对映体过量值达90％．     

手性二级胺催化的不对称串联反应研究进展

有机催化的不对称串联反应是快速构建复杂分子的重要的方法之一：利用简单易得的原料,在温和的反应条件下,经过简单的操作,高选择性地构建结构复杂的有机分子。近年来,使用手性二级胺催化的不对称串联反应取得了显著的进展,已经成为有机催化领域的一个研究热点。根据手性二级胺催化剂活化模式的不同,从亚胺～烯胺和烯胺一亚胺两种活化模式,对手性二级胺催化的不对称串联反应进行了综述,介绍了该领域最新研究进展。     

手性的控制：不对称有机催化——2021年诺贝尔化学奖成果简析

 2021年诺贝尔化学奖授予德国化学家Benjamin List和苏格兰裔美英籍化学家David MacMillan，以表彰他们在不对称有机催化领域的贡献。介绍了该诺奖工作的源头创新点和背景。阐述了手性化学、手性催化剂和不对称有机催化，及其对手性的控制。概括了有机催化和催化剂的类别。介绍了中国科学家和华人科学家在有机不对称催化领域的重要贡献，并对该领域的发展、研究现状和未来进行了展望。