手性有机小分子催化的最新进展*

手性有机小分子催化是近年来不对称催化领域发展起来的一个研究热点。手性有机小分子催化具有反应条件温和,环境友好,催化剂易于回收利用等优点,符合绿色化学的要求。本文根据手性有机催化剂活化模式的不同,从烯胺催化、亚胺催化、氢键活化、卡宾催化、相转移催化以及光化学等方面对近年来的有机小分子催化的进展,特别是中国学者的工作做一简要评述。重点通过对不同催化体系下催化剂和反应底物之间立体效应和电子效应的考察,发现控制反应立体选择性以及活化惰性底物的规律,进而设计更加高效的手性有机小分子催化剂,完善和拓展有机小分子催化的不对称合成。     

光诱导铁催化在有机合成中的应用研究进展

近年来,以过渡金属钌和铱络合物为代表的光催化剂的开发和应用为有机合成开启了新篇章,这些过渡金属光催化剂参与的光催化反应为化学键的构筑和有机转化提供了温和高效的新策略.为了丰富光催化剂的种类,拓宽光催化体系的适用范围,发展绿色可持续化学,近年来一些廉价易得的过渡金属比如铜、铁等被相继开发用作光催化剂.其中,铁催化剂因其无毒、种类丰富,并且具有独特的配体-金属电荷转移性质,在光催化合成领域大放异彩.依据反应类型对光诱导铁催化反应进行了综述,主要包括C—H键官能团化反应、C—C键官能团化反应、烯烃双官能团化反应、交叉偶联反应、脱羧官能团化反应、选择性氧化和还原反应.     

可见光催化需氧氧化在有机合成中的应用

可见光催化作为一种新兴且强大的有机合成手段,具有洁净节能、优秀的官能团兼容性和良好的化学选择性等特征。氧气作为一种廉价、无污染的氧化剂,与可见光催化相结合,极大地促进了绿色化学的发展。本文主要对我们课题组近年来在可见光需氧氧化领域取得的成果做了简明的综述,并对其发展进行了展望。     

α-氨基烷基自由基在可见光催化中的应用

可见光催化具有成本低及环境友好等特点,符合绿色化学的要求,近年来在有机合成领域引起了广泛关注.其中α-氨基烷基自由基因其具有活性高和易获得等优点,在可见光催化中占据着重要的位置.主要综述了该活性自由基在可见光催化中的发展和应用,并对其未来研究进行了展望.     

有机硒参与的硒环化反应研究进展

有机硒化物是一类重要的分子,在药物、农用化学品、有机材料以及催化等领域有着广泛的应用,在有机分子中引入硒原子在合成化学中具有重要意义.杂环化合物是构成多种生物活性分子的重要骨架,因此,合成含硒杂环衍生物的研究备受关注.分别描述了近年来快速发展的金属催化、电化学驱动、可见光驱动、有机分子催化以及其它类型的硒环化反应,并对...     

Fe和Co催化的碳-碳偶联反应的最新进展

作为廉价而且低毒的金属, Fe和Co是发展催化剂的理想元素. 同时由于Fe和Co有着多种氧化还原价态, 它们的催化化学应该具有极其丰富的内容. 然而由于种种原因, Fe和Co的催化剂很少得到有机化学家的关注. 直到最近几年, 人们才发现Fe和Co的催化剂可以很好地催化碳-碳偶联反应. 综述了Fe和Co催化碳-碳偶联反应的条件、产率和选择性; 探讨了这些新奇反应的可能机理; 并介绍了这些反应在复杂化合物合成中的应用.     

有机硒化物的反应及其在天然产物合成中的应用

有机硒化合物在有机合成，尤其是在天然产物的合成中，有着广泛而独特的应用。近年还发现，有些硒化合物本身就具有抗癌、抗病毒、防衰老等生理活性。因此，引起许多有机化学、生物化学和药物化学工作者的极大兴趣。有机硒化物这些重要价值，是由它的化学     

Corey化学酶的结构改造对催化性能的影响

综述了Corey化学酶的结构改造与催化性能之间关系,为有目的地选择和设计高效实用的手性催化剂用于有机不对称合成提供依据.     

在有机溶剂中酶催化的不对称反应

酶作为催化剂在有机合成中有着巨大的潜力,这在文献中有很多报道,但酶催化的反应作为经典的有机合成方法还很少,为什么呢?这是因为传统的合成方法以有机溶剂为介质而酶催化的反应以往要在水溶液中进行,另外,水会     

稀土化合物Yb(OTf)3催化的有机合成反应的最新进展

研究和开发环境友好的有机合成反应是"绿色化学"研究的一个重要内容,其中也包括新型绿色催化剂的研究.本文对近两年来Yb(OTf)3作为催化剂的有机合成反应按照反应类型进行了综述.进一步总结和拓展了Yb(OTf)3的催化范围,证明了稀土化合物广泛的应用前景.     

有机硒和碲化学的新进展

本文着重对最近几年来有机硒和碲化合物在有机合成中的应用进行了简要的综述。现在就硒和碲化合物作为反应试剂、在有机分子中引入硒和碲的方法以及从有机分中除去硒和碲的方法三个方面进行了讨论。由此也可见,有机硒和缔化合物在有机合成中的重要性。     

酶催化在聚合物合成中的应用进展

酶催化聚合反应条件温和、选择性高,引起了众多学者的关注。本文综述了酶催化方法在多糖、聚酯、聚碳酸酯、聚苯胺、聚烯烃和酚聚合物合成中的应用进展,并介绍了其在合成特殊结构聚合物方面的优势。虽然酶催化聚合反应具有良好的应用前景,但该类反应尚存在一些需要解决的问题,本文对此也进行了探讨。     

Asymmetric Syntheses Promoted by Organoselenium Reagents

Using chiral nonracemic electrophilic-organoselenium-reagents-asymmetric alkoxy-, hydroxy-, azido- and amido-selenenylation of alkenes were effected with high diastereoselectivity. These reagents have also been employed in catalytic amounts to promote one-pot selenenylation-deselenenylation processes. The asymmetric cyclization of properly substituted alkenes diastereoselectively afforded lactons, tetrahydrofurans oxazolines, thiazolines, pyrrolidines, isoxazolidines, 1,2-oxazines, and cyclic nitrones. Enantiopure dioxane, morpholine, tetrahydrofuran, oxazolidin-2-one and aziridine derivatives were prepared from alkenes, PhSeX, and optically active nucleophiles or substrates.     

Asymmetric Electrochemical Catalysis

Asymmetric electrochemical catalysis, an emerging frontline in asymmetric catalysis and electro-organic synthesis, is summarized. Representative works are classified, with respect to the external chiral resources, including chiral media, chiral mediator, chiral catalyst, and chiral electrode. This concept article is expected to provide readers with the general concepts and perspectives of each chiral electrochemical catalysis mode, and to indicate the potential and future development of asymmetric electrochemical catalysis.     

Recent Advances in Visible-Light Photoredox Catalysis for the Thiol-Ene/Yne Reactions

Visible-light photoredox catalysis has been established as a popular and powerful tool for organic transformations owing to its inherent characterization of environmental friendliness and sustainability in the past decades. The thiol-ene/yne reactions, the direct hydrothiolation of alkenes/alkynes with thiols, represents one of the most efficient and atom-economic approaches for the carbon-sulfur bonds construction. In traditional methodologies, harsh conditions such as stoichiometric reagents or a specialized UV photo-apparatus were necessary suffering from various disadvantages. In particular, visible-light photoredox catalysis has also been demonstrated to be a greener and milder protocol for the thiol-ene/yne reactions in recent years. Additionally, unprecedented advancements have been achieved in this area during the past decade. In this review, we will summarize the recent advances in visible-light photoredox catalyzed thiol-ene/yne reactions from 2015 to 2021. Synthetic strategies, substrate scope, and proposed reaction pathways are mainly discussed.     

“Green Is the Color”: An Update on Ecofriendly Aspects of Organoselenium Chemistry

Organoselenium compounds have been successfully applied in biological, medicinal and material sciences, as well as a powerful tool for modern organic synthesis, attracting the attention of the scientific community. This great success is mainly due to the breaking of paradigm demonstrated by innumerous works, that the selenium compounds were toxic and would have a potential impact on the environment. In this update review, we highlight the relevance of these compounds in several fields of research as well as the possibility to synthesize them through more environmentally sustainable methodologies, involving catalytic processes, flow chemistry, electrosynthesis, as well as by the use of alternative energy sources, including mechanochemical, photochemistry, sonochemical and microwave irradiation.     

Recent Advances in Covalent Organic Frameworks for Catalysis

Covalent organic frameworks (COFs) as an emerging type of crystalline porous materials, have obtained considerable attention recently. They have exhibited diverse structure and attractive performance in various catalytic reactions. It is highly expected to have a systematic and comprehensive review summing up COFs‐derived catalysts in homogeneous and heterogeneous catalysis, which is favorable to the judicious design of an efficient catalyst for targeted reaction. Herein, we focus on summarizing recent and significant developments in COFs materials, with an emphasis on both the synthetic strategies and targeted functionalization, and categorize it in accordance with the different types of catalytic reactions. Their potential catalysis applications are reviewed thoroughly. Moreover, a personal view about the future development of COFs catalysts with respect to the large‐scale production is also discussed.     

Catalysis for Oleochemical Platforms

The present review articles the most recent efforts, made in the Department of Chemical Sciences of the University of Naples Federico II, in the catalytic treatment of biomasses derived from vegetable oils. The review is focused on several technologies aimed at the production of either biofuels or valuable chemicals: (i) biodiesel production; (ii) esterification to obtain high-added value products; (iii) epoxidation of vegetable oils; (iv) glycerol ketalization; (v) oxidative cleavage of unsaturated fatty acids. The results are critically summarized to highlight the scientific activities and the main results in the field of biorefinery concept.     

Recent Advances in Supramolecular Gels and Catalysis

Over the past two decades, supramolecular gels have attracted significant attention from scientists in diverse research fields and have been extensively developed. This review mainly focuses on the significant achievements in supramolecular gels and catalysis. First, by incorporating diverse catalytic sites and active organic functional groups into gelator molecules, supramolecular gels have been considered as a novel matrix for catalysis. In addition, these rationally designed supramolecular gels also provide a variety of templates to access metal nanocomposites, which may function as catalysts and exhibit high activity in diverse catalytic transformations. Finally, as a new kind of biomaterial, supramolecular gels formed in situ by self‐assembly triggered by catalytic transformations are also covered herein.