有机电化学-电流驱动未来（英文）

电化学中最基本的作用力是电子-原子核之间的静电吸引力,它通过施加电势使电子加入或脱离与原子核的相互作用,因而,它是最经典的氧化还原化学.1800年第一个电池Volta Pile的发明实现了电子在电路中的流动,标志着有机电化学的开端.自19世纪以来,在科技革命的浪潮中,有机电化学合成取得了巨大发展,例如美国Manuel M.Baizer教授研究的丙烯腈电解还原二聚合成己二腈实现了工业化生产;纳尔科化学公司随后实现了四乙基铅的电化学工业化合成.这两个工业化案例的成功,使有机电化学合成进入了快速发展期.氧化还原是化学反应中的三大基本反应之一,对其进行研究,能极大地促进人类社会的发展.近年,有机合成工作者通过电化学策略代替传统氧化还原试剂实现了一系列氧化脱氢交叉偶联、还原偶联、金属介导的C-H键活化、不对称合成反应,极大地丰富了复杂化合物的合成方法库.有机电化学相比于传统的氧化还原化学,其采用无痕的电子作为氧化还原试剂,不仅廉价绿色,而且通过对电流、电压等方面的调节能高效地产生各种活性反应中间体,在复杂分子的合成中展现出极大的合成优势.本文主要从有机电化学反应机制优化以及跨学科新方法学的开发两...     

有机电化学合成的研究进展

有机电化学合成已成为一种实用、环境友好的合成方法, 广泛应用于氧化、还原以及氧化还原中性反应. 通过精准调控电流或者电位可在温和反应条件下实现一些具有挑战性的化学转化. 然而, 有机电化学反应也存在电极钝化、反应类型受限以及反应活性和选择性不易调控等难题. 日益紧张的能源和环境问题使得电化学合成近年来备受关注. 该综述的主要对象为有机溶液体系中的电化学合成, 从直接电解和间接电解两方面阐述近年来为解决这些难题所取得的进展. 在直接电解方面主要是通过合理的有机电化学反应设计、改变电解模式及设备或者将电化学技术与其它的化学合成技术相融合, 解决电极钝化、反应类型受限等问题. 在间接电解方面主要是利用有机分子或者过渡金属作为分子电催化剂去调控电极和底物之间的电子转移以及反应选择性, 实现一些选择性可控的化学转化.     

电化学合成C-磺酰基化合物的研究进展

磺酰基化合物是一类重要的有机硫化合物,在医药、农药和功能材料等领域中均具有广泛的应用,因此,有效的磺酰基化合物的合成策略已成为化学工作者们广泛研究的热点.有机电化学合成是一种绿色、温和、高效的合成策略,其在磺酰基化合物的合成中显示出了巨大的潜力.本综述介绍了近年来利用电化学手段合成C-磺酰基化合物的反应.按照电化学合成C(sp)-磺酰基化合物、C(sp²)-磺酰基化合物以及C(sp³)-磺酰基化合物的反应进行了分类归纳讨论,并对相应的反应机理进行了阐述,为今后此类反应在有机合成中的应用提供参考.     

重铬酸钾电化学合成反应表观动力学

针对重铬酸钾传统生产技术存在的高污染、高消耗等问题,研究了用电化学合成绿色技术.由在自制电解槽中以铬酸钾为原料电化学合成重铬酸钾的反应动力学实验,测得不同反应条件下的动力学数据.结果表明,电化学合成反应过程表现为拟零级反应动力学特征.建立了电化学合成反应表观动力学方程和阳极电解液体积随转化率的变化方程,求得了动力学参数...     

电化学条件下的Minisci反应研究进展

Minisci反应是指亲核性的碳自由基与缺电子含氮芳杂环间发生的自由基取代反应,是构建新的碳-碳键的一种重要方法.另一方面,作为一种绿色合成的技术和手段,有机电合成近几年来再次受到人们的关注.介绍了近期电化学条件下Minisci反应的研究进展.     

水相中邻苯二醌衍生物的电化学合成与原位转化

以绿色合成为目标的方法和技术是目前有机合成化学研究的重要内容。水相中的有机电化学合成兼有水相有机合成和有机电化学合成两种方法的优点,是一种重要的绿色合成技术,也是目前绿色化学研究的热点之一。研究表明,水相中邻苯二酚电化学氧化生成邻苯醌,该中间体非常活泼,可以与双烯发生[4+2]环加成反应生成烯酮衍生物,或者在亲核试剂的作用下,发生Michael加成反应生成取代邻苯二酚或者苯并杂环衍生物,而这些化合物常常具有各种抗菌、抗病毒(包括HIV)、抗肿瘤、保肝、扩冠等重要的生理作用。因此,水相中邻苯醌的电化学合成及其原位转化是一种有效的合成多羟基芳香化合物及其衍生物的方法。考虑到很多多羟基芳香化合物具有抗HIV整合酶的潜在活性,近三年来,我们开展了多羟基芳香族化合物电化学合成工作。本报告将简单介绍本课题组在这一方面的研究结果。     

有机氟化物的电化学合成

有机氟化物在很多领域(尤其是药物方面)有着广泛的应用,但鉴于氟的特殊反应性,氟原子的引入一直是有机化学中的难题.而有机电化学合成作为近年来新兴的合成手段,大大拓宽了有机反应的界限,使得更多绿色简易的氟化方法被开发了出来.本文就将集中列举这些有机电化学方法氟化的实例,并探讨电化学方法对于氟化学这一领域可能的推动作用.     

第9届全国有机电化学与工业学术会议征文通知

由中国化工学会精细化工专业委员会主办、厦门大学承办的第 9届全国有机电化学与工业学术会议 ,拟于 2 0 0 4年1 2月在厦门召开 ,届时将邀请国内外著名的专家、学者与会并作大会报告 ,同时进行专题讨论和学术交流 .会议主题是交流和展示我国有机电化学近两年来在基础研究、应用开发和产业化生产等方面的最新进展 ;展望和规划 2 1世纪我国有机电化学领域的发展前景 .1 .征文范围　有机电化学基础研究 ;有机电化学合成技术 ;有机电化学工业 ;电催化和修饰电极 ;有机电分析化学 ;有机光电化学 ;有机化学电源 ;新材料、新技术和绿色化学 .已正式…     

含硒杂环的电化学合成、分析及表征综合实验设计

化学综合实验是学生开展创新实践训练的重要课程。笔者结合团队的科研成果,设计了一个电化学合成含硒杂环的综合实验。实验通过底物制备→电化学合成分析→结构表征→晶体培养解析等环节,对学生的合成操作、过程分析和结构解析等技能进行系统训练。实验中的电化学合成思路有助于提升学生的绿色化学意识,激发实验学习兴趣。     

微波干介质反应

微波干介质反应是一门新兴的绿色化学合成技术,已成功地应用于多种有机反应。运用微波干介质反应技术进行一步法或多组分反应研究是当前库合成的研究热点。无溶剂反应具有成本低、操作简便、选择性好等优点,是绿色化学的重要研究方向之一。本文主要介绍了官能团的转化、氧化、还原、杂环化合物的合成、缩合及多组分反应等微波干介质反应。     

Recent advances towards electrochemical transformations of α-keto acids

As a kind of environmentally benign reagents, α-keto acids have been extensively employed as key starting materials in organic synthesis. Organic electrosynthesis has the advantages of reducing byproduct generation, improving the cost-efficiency of synthetic processes, and accessing reactive intermediates under mild conditions. Inspired by the merits of organic electrosynthesis, α-keto acids have shown many synthetic applications in electrochemical acylation, cyclization, and reductive amination reactions with improved efficiencies and selectivities. This review covers the recent breakthroughs achieved in the electrochemical transformations of α-keto acids, aimed at highlighting these electrochemical reactions’ features and mechanistic rationalisations. Meanwhile, the practicalities and limitations of these transformations are also presented where possible.     

有机电化学合成简谈

本文简要介绍了有机电化学合成的体系,研究方法和技术及主要特征。以C=C类物质为例介绍了有机电化学合成中的各类反应,并以己二腈的电合成为例介绍了相应的工业化应用。试图以CO2的电化学固定利用为例介绍了有机电化学合成的研究动向。     

Versatile Use of Carbon Dioxide in the Synthesis of Carbamates

Summary. Organic carbamates classically have been synthesized using harmful and toxic reagents like phosgene, its derivatives, and carbon monoxide. Recently, carbon dioxide was used as a cheap and harmless reagent for the synthesis of organic carbamates in the gaseous or supercritical state, or in an electrochemical process, or organic carbonates as sources of carbon dioxide as an alternative to the harmful reagents. The present review will deal with the extensive use of carbon dioxide in the synthesis of organic carbamates.     

Comprehensive Comparisons between Directing and Alternating Current Electrolysis in Organic Synthesis

Organic electrosynthesis has consistently aroused significant interest within both academic and industrial spheres. Despite the considerable progress achieved in this field, the majority of electrochemical transformations have been conducted through the utilization of direct-current (DC) electricity. In contrast, the application of alternating current (AC), characterized by its polarity-alternating nature, remains in its infancy within the sphere of organic synthesis, primarily due to the absence of a comprehensive theoretical framework. This minireview offers an overview of recent advancements in AC-driven organic transformations and seeks to elucidate the differences between DC and AC electrolytic methodologies by probing into their underlying physical principles. These differences encompass the ability of AC to preclude the deposition of metal catalysts, the precision in modulating oxidation and reduction intensities, and the mitigation of mass transfer processes.     

From polymer to small organic molecules: a tight relationship between radical chemistry and solid-phase organic synthesis

Since Gomberg's discovery of radicals as chemical entities, the interest around them has increased through the years. Nowadays, radical chemistry is used in the synthesis of 75% of all polymers, inevitably establishing a close relationship with Solid-Phase Organic Synthesis. More recently, the interest of organic chemists has shifted towards the application of usual "in-solution" radical chemistry to the solid-phase, ranging from the use of supported reagents for radical reactions, to the development of methodologies for the synthesis of small molecules or potential libraries. The aim of this review is to put in perspective radical chemistry, moving it away from its origin as a synthetic means for solid supports, to becoming a useful tool for the synthesis of small molecules.     

Recent Advances in Organic Electrochemical C—H Functionalization

Organic electrochemistry has a rich history in organic synthesis and has been considered as a promising alternative to traditional chemical oxidants and reductants because it obviates the use of stoichiometric amount of dangerous and toxic reagents. In particular, the electrochemical C—H bonds functionalization is one of the most desirable approaches for the construction of carbon–carbon (C—C) and carbon–heteroatom (C—X) bonds. This review summarizes the substantial progress made in the last few years in C—H functionalization via organic electrochemistry. It is divided into sections on C—C, C—N, C—O, C—S, C–Halogen and C—P bond formation.     

钐试剂在有机合成中的应用

钐试剂在有机合成中的应用是近年来有机合成方法学研究中的热点之一。综述了十余年来本课题组在钐试剂应用于有机合成方面所开展的有关工作：(1)二碘化钐作为偶联剂和还原剂在有机合成中的应用;(2)金属钐直接应用于有机合成;(3)三碘化钐作为路易斯酸应用于有机合成;(4)有机钐试剂在有机合成中的应用。     

Directing transition metal-based oxygen-functionalization catalysis

This review presents the recent progress of oxygen functionalization reactions based on non-electrochemical (conventional organic synthesis) and electrochemical methods. Although both methods have their advantages and limitations, the former approach has been used to synthesize a broader range of organic substances as the latter is limited by several factors, such as poor selectivity and high energy cost. However, because electrochemical methods can replace harmful terminal oxidizers with external voltage, organic electrosynthesis has emerged as greener and more eco-friendly compared to conventional organic synthesis. The progress of electrochemical methods toward oxygen functionalization is presented by an in-depth discussion of different types of electrically driven-chemical organic synthesis, with particular attention to recently developed electrochemical systems and catalyst designs. We hope to direct the attention of readers to the latest breakthroughs of traditional oxygen functionalization reactions and to the potential of electrochemistry for the transformation of organic substrates to useful end products.

This review presents the recent progress of oxygen functionalization catalysis via non-electrochemical (conventional organic synthesis) and electrochemical routes.     

烯酸在有机高价碘试剂催化下的氯代内酯化反应

研究了不饱和烯酸在有机高价碘催化剂和间氯过氧苯甲酸作用下与氯化锂的反应. 通过该反应, 4-戊烯酸等可在常温下短时间内得到良好产率的氯代γ-丁内酯化合物, 提供了简单快速合成氯代γ-丁内酯的新方法. 考察了反应条件的影响, 并提出了可能的反应机理.     

Simple and Versatile Nitrooxylation: Noncyclic Hypervalent Iodine Nitrooxylating Reagent

Organic nitrates are broadly applied as pharmaceuticals (acting as efficient nitric oxide donor), energetic materials, building blocks in organic synthesis, etc. However, practical and direct methods to access organic nitrates efficiently are still rare, mainly due to the lack of powerful nitrooxylating reagents. Herein, we report bench-stable and highly reactive noncyclic hypervalent iodine nitrooxylating reagents, oxybis(aryl-λ³-iodanediyl) dinitrates (OAIDNs, 2 ), which are prepared just by using aryliodine diacetate and HNO₃. The reagents are used to achieve a mild and operationally simple protocol to access diverse organic nitrates. By employing of 2 , zinc-catalyzed regioselective nitrooxylation of cyclopropyl silyl ethers is realized efficiently to access the corresponding β-nitrooxy ketones with high functional-group tolerance. Moreover, a series of direct and catalyst-free nitrooxylations of enolizable C−H bonds are carried out smoothly to afford the desired organic nitrates within minutes by just mixing the substrates with 2 in dichloromethane.