实用化导向的X射线晶体学与结构解析教学改革探索

结构决定性能。物质结构是当代化学、材料、生物学科前沿探索的基石和导引,测定解析物质结构是很多科研工作者必备的技能和研究手段。X射线衍射是结构测定最常见的方法之一。在科研一线工作的师生对X射线晶体学知识和结构解析技能有着大量的需求。然而,当前国内高校开设专业X射线晶体学课程较少,课程内容理论性强,实践环节不足,不能完全满足非晶体专业方向学生需求。面对X射线衍射结构解析的实际问题,学生难以从传统课程和导师等渠道得到足够支持帮助,需求和供给存在缺口。本文分析国内X射线晶体学教学和知识传播现状以及存在的问题,从知识提升、技能培养和信心树立三个方面针对性地改革X射线晶体学与结构解析的教学方式和内容,通过将传统课程拆分为X射线衍射原理、简明晶体学和结构解析技术三部分,扩充实践内容环节,特别是晶体数据收集和结构解析精修的要点技巧,辅以必要的基础理论知识,有效补充广大非晶体专业方向师生亟需的X射线晶体学基础知识和结构解析技术,围绕学生科研一线实际需要,以提升实战技能来解决学生的痛点和难点,同时树立学生面对结构解析的自信心。

手性双氮氧/金属配合物催化叶立德不对称反应的研究进展

叶立德作为内盐分子,活性高、种类和反应类型多样,极具吸引力,是合成含杂原子化合物的重要工具.另一方面,冯氏手性双氮氧配体作为优势配体,结构高度可调,与主族、过渡金属和稀土金属等形成配合物已催化众多不对称反应.本文介绍了手性双氮氧/金属配合物作为路易斯酸催化剂、与过渡金属或光敏试剂组合催化等方式,实现硫叶立德、氮叶立德和碘叶立德的不对称转化,涉及不对称加成、环化、重排、串联等,并重点关注关键的反应过程和手性诱导机理.最后,展望了手性双氮氧/金属配合物催化叶立德不对称反应的挑战和前景.

Catalytic Asymmetric[3+2]Cycloaddition of Exocyclic Enol Ethers for the Synthesis of Spiroketals

An efficient synthesis of chiral benzannulated spiroketals via catalytic asymmetric[3+2]cycloaddition of exocyclic enol ethers with p-quinones was achieved.The transformation was enabled by a chiral N,N′-dioxides/Tm^(Ⅲ)complex as the Lewis acid catalyst and afforded a series of enantiomerically enriched benzannulated spiroketal derivatives in good yields(up to 99%)and enantioselectivities(up to 98%ee).Topographic steric maps and distribution of the buried volumes of the catalysts via Cavallo’s SambVca 2 tool were used to elucidate the enantioinduction raised by the ligands and the metal ions.

手性双氮氧配体及其金属配合物不对称催化

不对称催化是获得手性物质最高效的方法之一.针对效率和选择性的核心问题,发展高效高选择性的手性配体和催化剂是关键.不对称催化经过几十年的发展,其中手性金属配合物催化最受关注,应用也最广泛,但优势手性配体极其有限.因此,创制高效高选择性的优势手性配体是不对称催化领域最重要和最具挑战性的目标.在过去20年里,冯小明团队一直潜心催化不对称合成方面的研究,设计、合成了一类全新的具有柔性构象的手性双氮氧-酰胺化合物,被公认为一类优势手性配体和催化剂,打破了传统优势配体刚性构象的要求.建立了手性双氮氧-金属配合物催化剂库,高效高选择性实现了50多类重要的不对称反应,尤其是一些不对称催化新反应,为多个手性药物分子和天然产物的合成提供了简单、高效、精准、绿色途径.本文介绍了该类配体和催化剂的设计、合成以及手性双氮氧金属配合物催化的代表性不对称反应.这些原创性和系统性的研究工作,为手性科学的快速发展作出了重要贡献.

Chiral organobases: Properties and applications in asymmetric catalysis

Chiral organobases occupy a significant position in asymmetric organocatalysis. The general types of chiral organobases include tertiary amines, amidines, guanidines, cyclopropenimines, and iminophosphoranes, etc. These organobases are demonstrated to be effective organocatalysts to promote divers kinds of base-initiated reactions in excellent yields and stereoselectivities. In previous reports, several groups have summarized each kind of chiral organobases in different reviews. To the aim of understanding the whole of them in one review, herein, we provide a brief introduction of these chiral organobases in asymmetric catalysis.

Asymmetric catalytic nitrooxylation and azidation of β-keto amides/esters with hypervalent iodine reagents

Chiral Lewis acid-catalyzed enantioselective nitrooxylation of cyclic and acyclicβ-keto amides/esters with hypervalent iodine(III)reagents is reported.A number ofα-nitrooxy-β-keto amides/esters were obtained with good yields and high enantioselectivities by using bench-stable nitratobenziodoxole under mild conditions.

Synthesis of Dihydroisoquinoline and Dihydropyridine Derivatives via Asymmetric Dearomative Three-Component Reaction

We report the first asymmetric three-component nucleophilic addition/dearomative[4+2]cycloaddition/isomerization cascade of transient dipoles generated from N-heteroarenes and allenoates with methyleneindolinones in the presence of chiral N,N′-dioxide/metal complexes.This tandem reaction enabled rapid access to versatile chiral polycyclic N-heterocycles with good to excellent enantioselectivities under mild reaction conditions in spite of the strong background reaction,including 1,2-dihydroisoquinoline,1,2-dihydropyridine derivatives,and others.Meanwhile,a series of control experiments were conducted to elucidate the reaction mechanism and the roles of additives.

Ligand Acceleration in Chiral Lewis Acid Catalysis

Ligand-accelerated catalysis(LAC),a term originally coined by Sharpless,has been a pivotal guiding principle in the advancement of asymmetric catalysis.The discovery and understanding of LAC have not only energized the enhancement of established catalytic asymmetric transformations but also ignited the creation of novel ones.In this review,we have curated a selection of illustrative examples,delving into the profound influence that chiral ligands exert on the acceleration of Lewis acid-promoted reactions,encompassing both thermally induced and photochemical processes.The impact of a chiral ligand on various facets,including solubility,aggregation state,geometry,Lewis acidity,and photophysical properties of metal salts,has been identified as crucial determinants.Moreover,the covalent and noncovalent interactions between ligands and substrates,the creation of chiral pockets by chiral ligands and metals,as well as the alterations in the physical and chemical properties of substrates induced by Lewis acid coordination,also play significant roles.Notably,the utilization of ligandaccelerated asymmetric Lewis acid catalysis in photoreactions presents an efficient approach for addressing the challenges associated with stereocontrol.We anticipate that this review will inspire researchers to pay more attention to the role of ligands and aid in the development of new efficient ligands and asymmetric reactions.