具有生物活性的4-色满酮衍生物的合成进展

4-色满酮衍生物在自然界中广泛存在,大多数都具有生物活性。具有生物活性的4-色满酮衍生物又大多具有手性,尤其C2位置。有关它们的不对称合成引起了有机合成工作者的广泛关注。C2(手性)-4-色满酮衍生物合成的关键是C2手性中心的控制合成。本文根据4-色满酮衍生物构建方式的不同进行分类,概述了近十几年来合成C2(消旋或手性)4-色满酮衍生物的最新方法, 侧重讨论了合成立体结构专一的C2(手性)-4-色满酮的反应特点。     

具有生物活性的4-色满酮衍生物的合成研究进展

4-色满酮衍生物广泛存在于自然界中,大多数都具有生物活性。具有生物活性的4-色满酮衍生物又大多具有手性,尤其是C_2位置,有关它们的不对称合成引起了有机合成工作者的广泛关注。C_2手性-4-色满酮衍生物合成的关键是C_2手性中心的控制合成。本文根据合成方式的不同进行分类,概述了近十几年来合成C_2消旋或手性4-色满酮衍生物的最新方法,侧重讨论了合成立体结构专一的C_2手性-4-色满酮的反应特点。     

6-氟-色满酮-2-羧酸(酯)的选择催化氢化

具有色满环结构单元的化合物广泛应用于医药、香料和化妆品中[1].在临床上,这类衍生物做为钾离子和钙离子通道调节剂对心脏和血压起调节作用[2];有些化合物还表现出抗HIV和抗肿瘤活性[3].6-氟-色满-2-羧酸(酯)类衍生物在合成具有上述生物活性的化合物时可做为中间体被应用.     

手性4-取代色满骨架的立体选择性构建研究进展

手性4-取代色满骨架在很多具有生物活性的天然产物及其类似物中广泛存在,该骨架的不对称构建策略在新药开发中扮演着重要角色。本文从加成反应、氢化反应、烷基化反应、烯/炔丙基化反应、去对称化反应、羰基α位芳基化反应和重排反应七个方面综述了手性4-取代色满骨架的立体选择性构建策略,以期为含有该类骨架的活性天然产物的不对称合成提供参考。     

色满螺哌啶衍生物的合成及生物活性研究进展

色满螺哌啶是一类特殊的三环骨架,其通过结构修饰可发展一系列衍生物,从而表现出广泛的生物活性,如抗肿瘤、抗菌、抗疟、抗肥胖、抗炎、抗氧化以及抗精神病等。因此,色满螺哌啶衍生物在有机合成和医药研发领域中发挥了重要的作用。本文主要介绍在色满的C2位和哌啶环的C4′位稠合而成的色满螺哌啶类衍生物,包括螺[色满-2,4′-哌啶]类、螺[色满-2,4′-哌啶]-4(3H)-酮类、螺[色烯-2,4′-哌啶]类和螺[苯并[b][1,4]噁氮杂?-2,4′-哌啶类化合物等,简述这四类衍生物的经典合成方法,并重点对其生物活性研究进展进行评述。     

松香树脂酸及其衍生物的生物活性研究进展

松香树脂酸是一种重要的天然可再生资源,具有独特的化学结构和多个手性中心,表现出广泛的生物活性,在医药及农药等领域有着重要的用途.本文按照松香树脂酸衍生合成的特点,对松香树脂酸及其衍生物的生物活性研究进展进行了综述,并对松香树脂酸及其衍生物的生物活性研究前景进行了展望.     

茚及其衍生物的催化不对称合成

茚及其衍生物广泛存在于自然界中,其中多官能团化的茚类化合物大多具有重要的生物活性,因而非常具有成为药物的先导化合物的潜力。特别是茚类化合物的不对称合成吸引了有机化学家们的广泛关注,最近有许多相应的合成方法研究被报道,包括外消旋体拆分、手性辅基及底物诱导的合成和手性催化合成等。本文总结了茚及其衍生物的催化不对称合成研究进展,重点介绍过渡金属及有机小分子不对称催化反应,并对该领域的研究前景进行了展望。     

吲哚氮杂环作为自由基受体在串联环化反应中的研究进展

含吲哚骨架衍生物因其具有多样的生物活性,广泛应用于生物活性分子的合成与修饰,特别是在药物化学、农药化学领域中.近年来,高效的吲哚环合成与后官能化反应己成为热门的研究主题,例如吲哚的不对称去芳构化反应构建螺环衍生物.不饱和烃的自由基串联反应一直是有机化学的一个重要研究分支,含吲哚母体的不饱和烃串联环化反应已经成为吲哚骨架...     

N-环钯化二茂铁衍生物的合成和应用（英文）

近年研究表明二茂铁的环钯化衍生物被广泛地应用于各类偶联反应中,比如Heck反应、Suzuki反应、aza-Claisen重排反应等.主要综述了含氮导向基的二茂铁衍生物的环钯化反应,包括通过不对称诱导或拆分手段合成具有平面手性环钯化合物,基于环金属化反应1,1'-取代二茂铁钯化物的合成,以及其在催化反应的应用.     

手性磷酸催化的C（3）-取代吲哚和甲基乙烯基酮不对称串联反应

3位含有季碳手性中心的吲哚啉并环化合物是一类非常重要的化合物, 广泛存在于各种天然产物和具有生物活性的分子中. 化学家们发展了多种有效的途径来合成这类化合物. 其中以方便易得的吲哚衍生物为起始原料, 利用不对称去芳构化\环化串联的方法最为简单高效, 但多数工作都是从色胺或色醇衍生物出发, 合成二氢吡咯并吲哚啉或二氢呋喃并吲哚啉化合物. 因此, 发展其他类型的吲哚衍生物的不对称去芳构化\环化反应显得非常有必要. 作者课题组发展了手性磷酸催化的吲哚衍生物与甲基乙烯基酮的不对称Michael加成\环化串联反应. 以5 mol% (R)-SPINOL为骨架的手性磷酸(R)-4c为催化剂, 以中等到良好的收率和优秀的对映选择性构建了一系列手性吲哚[2,3-b]并氢化喹啉化合物, 而且该催化体系对于克级规模反应同样能够获得很好的结果.     

Rh-catalyzed intramolecular aromatic C–H insertion of α-diazo β-ketoesters: synthesis of 4-carbonyl chroman derivatives

A Rh-catalyzed intramolecular aromatic C–H insertion of α-diazo β-ketoesters was developed. This protocol offers a practical strategy for the synthesis of 4-carbonyl chroman derivatives with high yield and is compatible with a wide variety of substituents. Synthetic applications of the 4-carbonyl chroman were also demonstrated.     

固定化脯氨酸及其衍生物用于催化不对称有机合成

脯氨酸及其衍生物作为有机手性催化剂,在不对称有机合成中得到广泛应用。该类催化剂具有结构简单、来源丰富和选择性高等优点,但仍存在催化剂用量大、难以回收以及无法重复利用等不足。近年来,随着固定化技术的发展,固定化脯氨酸及其衍生物受到广泛关注。固定化脯氨酸及其衍生物催化剂可以简化不对称催化中产物的分离过程,实现催化剂的便利回收与循环使用。本文综述了固定化脯氨酸及其衍生物的制备及在催化不对称有机合成(如Aldol反应、Michael加成反应、Mannich反应等)中的研究进展。     

有机催化不对称Michael加成反应

有机催化的不对称合成反应是目前研究最为活跃的领域之一. 不对称Michael加成反应是合成众多重要的手性合成子和药物中间体的有效手段. 目前报道的催化Michael加成反应的有机催化剂主要有脯氨酸及其衍生物、手性咪唑啉酮、手性(硫)脲、金鸡纳碱衍生物等. 对各类有机催化剂在有机催化不对称Michael加成反应中的应用, 以及不对称诱导反应的机理、催化剂分子结构及反应条件对其催化活性和不对称诱导作用的影响进行了评述.     

Synthesis and applications of optically active metallacycles derived from primary amines

The synthesis of optically active cyclopalladated derivatives containing primary amines and their application as resolving agents of Lewis bases is reviewed. Some other applications such as the determination of the absolute configuration of coordinated chiral phosphines and the synthesis of chiral liquid crystals are also presented.     

Convenient divergent strategy for the synthesis of TunePhos-type chiral diphosphine ligands and their applications in highly enantioselective Ru-catalyzed hydrogenations

A convenient, divergent strategy for the synthesis of a series of modular and fine-tunable C3-TunePhos-type chiral diphosphine ligands and their applications in highly efficient Ru-catalyzed asymmetric hydrogenations were explored. Up to 97 and 99% ee values were achieved for the enantioselective synthesis of beta-methyl chiral amines and alpha-hydroxy acid derivatives, respectively.     

Pd(II)-catalyzed asymmetric Wacker-type cyclization for the preparation of 2-vinylchroman derivatives with biphenyl tetraoxazoline ligands

This article describes an efficient method for the preparation of chiral chroman derivatives by the Pd(II)-catalyzed asymmetric Wacker-type cyclization using a chelation-induced axially chiral tetraoxazoline ligand. Under the optimized conditions, up to 80% yield and up to 92% ee were obtained. This is the first example to utilize o-trisubstituted 3-butenylphenols as substrates in such transformation.     

Chiral benzimidazoles and their applications in stereodiscrimination processes

Chiral aspects of benzimidazoles have been over-shadowed for a long time due to the large number of reports on benzimidazoles in the medical field in numerous categories of therapeutic agents. The vigorous research activity in chiral applications of benzimidazole derivatives started after bifunctional benzimidazoles made their appearance especially in the last 2–3 decades. Thus, chiral benzimidazoles form a comparatively young branch of chiral chemistry. The presence of pyridine and pyrrole type of nitrogens along with the fused benzene ring confer on this class of molecules, special properties including useful nucleophilicity, hydrogen bonding ability and a rigid backbone, all of which play decisive roles in proven chiral applications. The present review aims to cover the synthetic routes to access chiral benzimidazoles and their applications in a plethora of chiral fields including enantioselective organocatalysis, metal-based catalysis, asymmetric transformations involving benzimidazole-N-heterocyclic carbenes, kinetic resolution, benzimidazole-based macrocyclic hosts in chiral supramolecular chemistry and other miscellaneous chiral applications.     

L-脯氨酸衍生物为手性侧链的新型C_2对称型手性固定相

绕轴旋转180°能与自身重合的C_2对称型手性化合物在手性催化和手性分离领域有重要应用。以L-脯氨酸苯基酰胺衍生物为手性源,合成了一类新型的C_2对称型手性固定相,并进行了手性色谱拆分评价。与单侧链取代的刷型固定相进行对比,C_2对称型手性固定相对所评价的31种酸性、中性和碱性分析物表现出更好的手性选择性。考察了固定相末端苯环上的取代基团对手性拆分的影响,综合来看,苯环上无取代基的C_2对称型手性固定相的分离性能最优。对某些手性对映体,C_2对称型手性固定相的分离因子随温度的增高而呈现异常增大的现象,表明了其有别于单侧链取代的固定相的分离机理。该类新型手性固定相的提出对进一步丰富刷型手性固定相的种类和拓展其应用具有重要意义。     

General access to asymmetric γ-cyclodextrins for gas chromatographic applications by insertion of a selectively modified sugar unit

Gas chromatography (GC) using chiral stationary phases (CSPs) based on modified cyclodextrins is the most commonly used technique to quantify enantiomeric purity of synthesized volatile racemic drugs. The fully methylated cyclodextrin derivatives are the most used because of their easy synthesis, their thermal stability and their ability to recognize a wide range of compounds. To complete the background on molecular recognition, we describe a route to access fully characterized new asymmetric cyclodextrins derived from fully methylated ones, thereby directly useful in chiral gas chromatography. The synthesis of these compounds involves a three-step procedure: ring opening of fully methylated cyclodextrins, elongation of the chain with correctly modified monosaccharide derivatives and, finally, macrocyclization to obtain the desired compounds. This strategy is applied to achieve the synthesis of a series of asymmetric γ-cyclodextrins, by insertion of glucopyranosic derivatives. Appropriate selection of the glycosylating reagents during chain elongation and macrocyclization steps allows satisfactory anomeric selectivities to be reached.     

Chiral thiophene derivatives with optimal two‐photon absorption in near‐infrared window I and II

Thiophene derivatives are outstanding organic materials due to their wide spectral response, superior optoelectronic properties, and excellent environmental stability, which have attracted widespread attention in both theory and applications. However, their chiral analogues and corresponding chiroptical behaviors have been rarely investigated. Herein, a series of chiral thiophene derivatives are firstly designed by taking both optical chirality and two‐photon absorption (TPA) response into consideration, and are then investigated by modern analytical response theory. The calculated results demonstrate that these novel chiral thiophene derivatives show optimal TPA in the near‐infrared (NIR) window I and II, indicating that they are promising for biological applications. More importantly, they exhibit reasonable two‐photon circular dichroism (TPCD) signals, which are desirable candidates for chiral recognition regions. Furthermore, the calculations of orbital transitions shed light on that the intramolecular charge transfer plays an important role in their excellent TPA and TPCD behaviors in NIR regions.