Fluorinated Alcohols: Magic Reaction Medium and Promoters for Organic Synthesis

Fluorinated alcohols have been widely used in the synthetic organic chemistry over the past decades. The unique properties such as the strong hydrogen‐bonding donor ability and low nucleophilicity allow them to promote organic reactions in the absence of any catalyst. These approaches have distinct advantages in terms of operational simplicity, practicability and environmental friendliness. Reactions promoted by fluorinated alcohols, including nucleophilic substitution reactions, annulation reactions, electrophilic reactions, dearomatization reactions, functionalization of multiple bond, epoxidation reactions and miscellaneous reactions have been summarized in this account.     

Benzothiazoles from Condensation of o-Aminothiophenoles with Carboxylic Acids and Their Derivatives: A Review

Nowadays, organic chemists are interested in the field of heterocyclic chemistry due to its use in the synthesis of a great variety of biologically active compounds. Heterocyclic compounds are widely found in nature and are essential for life. Among these, some natural nitrogen containing heterocyclic compounds have been used as chemotherapeutic agents. Their attachment to sugar molecules either as thioglycosides or as nucleosides analogues plays an important role in vital biological processes as well as in synthetic organic chemistry. Molecules containing benzothiazole (BT) nuclei are of this interesting class of compounds because some of them have been found to have a wide variety of biological activities. In this sense, we selected this topic to review and to then summarize the procedures related to the condensation reactions of o-aminothiophenoles (ATPs) as well as their disulfides with carboxylic acids, esters, orthoesters, acyl chlorides, amides, and nitriles. The condensation reactions with carbon dioxide (CO₂) are included. Conventional methods with the use of acid and metal catalysts as well as recent green techniques, such as microwave irradiation, the use of ionic liquids, and ultrasound (US) chemistry, which have proven to have many advantages, were found in the review.     

C-Phosphanylated sulfoximines: synthesis and applications in asymmetric allylic substitution reactions

Starting from cyclic sulfonimidates, a number of C-phosphanylated enantiomerically pure sulfoximines have been prepared either as such or in protected form. Two of them, 5a and epi-5a, have been used as ligands in palladium complex catalyzed allylic substitution reactions delivering the substitution product with up to 95% ee.     

Synthesis, characterization, and reactions of 6,13-disubstituted 2,3,9,10-tetrakis(trimethylsilyl)pentacene derivatives

Pentacene has been actively studied as relevant materials in organic field-effect transistors (OFETs) and organic light-emitting diodes (OLEDs). However, the low solubility and low stability of pentacene in common organic solvents have hindered its applications. When exposed to light or at high concentration, pentacene is found to dimerize easily. Many research groups are currently working on the design and synthesis of novel substituted pentacenes, but few of them systematically reported physical properties such as molecular spectroscopy and electronic properties, which might elucidate the influence of substituents on HOMO-LUMO gaps. Furthermore, the reactive nature of the central ring in pentacenes makes pentacenes good dienes for Diels-Alder reactions. In this paper, a series of soluble 6,13-disubstituted 2,3,9,10-tetrakis(trimethylsilyl)pentacenes were synthesized and characterized. Their reactions, structures, and physical properties were also studied. In addition, bulky o-carboranyl substituted pentacene derivative 15 and 6-chloro-2,3,9,10-tetrakis(trimethylsilyl)pentacene (16) were synthesized for the first time. Compound 16 possesses the largest dihedral angle (7.7° with two adjacent benzene rings) and shows a wave structure. Diels-Alder reactions with acceptable efficiency were carried out between 16 and various dienophiles.     

Single-atom catalysis for organic reactions

Metal-based catalysis, including homogeneous and heterogeneous catalysis, plays a significant role in the modern chemical industry. Heterogeneous catalysis is widely used due to the high efficiency, easy catalyst separation and recycling. However, the metal-utilization efficiency for conventional heterogeneous catalysts needs further improvement compared to homogeneous catalyst. To tackle this, the pursing of heterogenizing homogeneous catalysts has always been attractive but challenging. As a recently emerging class of catalytic material, single-atom catalysts (SACs) are expected to bridge homogeneous and heterogeneous catalytic process in organic reactions and have arguably become the most active new frontier in catalysis field. In this review, a brief introduction and development history of single-atom catalysis and SACs involved organic reactions are documented. In addition, recent advances in SACs and their practical applications in organic reactions such as oxidation, reduction, addition, coupling reaction, and other organic reactions are thoroughly reviewed. To understand structure-property relationships of single-atom catalysis in organic reactions, active sites or coordination structure, metal atom-utilization efficiency (e.g., turnover frequency, TOF calculated based on active metal) and catalytic performance (e.g., conversion and selectivity) of SACs are comprehensively summarized. Furthermore, the application limitations, development trends, future challenges and perspective of SAC for organic reaction are discussed.     

Recent development of ortho-C–H functionalization of aryl sulfoxides through [3,3] sigmatropic rearrangement

Sulfoxide-promoted ortho-C–H functionalization reactions of aromatic compounds have emerged as powerful tools for organic synthesis. Among them, [3,3] sigmatropic rearrangement induced by interrupted Pummerer reaction or electrophilic activation of sulfoxides has proved to be a fruitful strategy due to its versatility and high reaction efficiency. This digest paper mainly focuses on recent progress on C–H functionalization reactions of aryl sulfoxides via [3,3] sigmatropic rearrangement of sulfonium-tethered intermediates.     

Cycloaddition reactions in aqueous systems: A two-decade trend endeavor

Cycloaddition reactions are an integral and weighty part of organic chemistry in pedagogy and research as well. The wealthy literature on cycloaddition reactions from their birth up to now, unequivocally witnesses to their leading chemistry. The so-called “conventional solvents” are organic solvents that have indubitably promoted their success. Yet, the toxicity facet of these solvents impedes their use freely and with no fear. Not only is the operating chemist uncomfortable while experimenting, but also the environment is equally threatened. Working out the cycloaddition reactions and other organic ones in aqueous systems would certainly bring some relief to the chemist and to the environment as well. Unusual outcomes in terms of yield, reactivity and selectivity compared to those performed in organic solvents were commonly observed, and have overwhelmed the chemists with surprise indeed. In this review, homo Diels–Alder reactions in aqueous media include those involving the following dienophiles: maleimides, α,β-unsaturated esters, p-benzoquinones, vinyl ketones, phenyl-1-(2-pyridyl)-2-propen-1-one, α,β-unsaturated esters. A special case is the organocatalysis of Diels–Alder cycloaddition of α,β-unsaturated ketones (aldehydes). Of no less importance, some hetero Diels–Alder cycloaddition reactions in water systems are delineated. The impact of additives (salts, organic and inorganic chemicals), micellar catalysis and Lewis/Brønstëd acid catalysis on outcomes of such cycloaddition reactions is discussed. The 1,3-dipolar cycloaddition methodology applied to aqueous media has brought forth a number of heterocyclic compounds, usually with a regio- and stereoselectivity pecularity. These heterocycles include triazoles, tetrazoles, pyrazoles, isoxazoles, isoxazolidines, pyrroles and pyrrolidines. The superiority of copper(I) catalysis in the azide-alkyne cycloaddition (Huisgen cycloaddition) in water is endorsed by a number of examples.     

Recent advances in the synthesis and CF functionalization of gem-difluoroalkenes

The gem-difluoroalkenes and related compounds have gained much attention from the organic synthetic community due to their widespread applications as versatile fluorinated building blocks for the synthesis of pharmaceuticals, agrochemicals and functional materials. In the past two decades, significant progress has been made to the development of efficient methods for the construction of gem-difluoroalkenes and useful reactions involving the cleavage of CF bond in gem-difluoroalkenes. In this Digest review, these advances in the synthesis and reaction chemistry of gem-difluoroalkenes are summarized, with special emphasis placed on novel synthetic applications of them in recent ten years.     

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.     

Recent advancements in palladium-catalyzed reactions involving molecular oxygen

Oxidation reactions have significant value in organic chemistry, having been in focus continuously due to the high efficiency in building up molecular complexity. In the past few decades, transition metal-catalyzed oxidation reactions have been significantly explored and have played important roles in organic synthesis. Compared to the widely-used oxidants, such as inorganic salts, peroxides, hypervalent iodine reagents and quinones, molecular oxygen (O₂), which is natural, inexpensive, and environmentally friendly, is a highly appealing oxidant in academic and industry area for green and sustainable chemistry. Recently, significant advances have been made in palladium-catalyzed reactions using O₂ as the oxidant. This critical review highlights some of the recent developments in molecular oxygen-involved Pd-catalyzed oxidation reactions with a focus on mechanistic strategies and new reaction developments.     

Transition-metal-free coupling reactions involving gem‑diborylalkanes

Due to the increasing demand for the sustainability of modern organic chemistry, the development of green and powerful methods for C-C and C-B bond formation is highly desired. Among them, the transition-metal-free coupling reactions of gem‑diborylalkanes emerge as one valuable tool for organic chemists in the last decade. The review covers selected representative examples. A comparison of these reactions with transition-metal-catalyzed reactions is provided. The recent example of α-boryl radical formation from gem‑diborylalkanes is also briefly discussed.     

催化反应中休眠期与诱导期之区别

许多化学反应中都存在一个被定义为"诱导期"的起始反应速率较低的阶段，例如一些自由基反应、放热反应和催化反应。与之相比，在极少数的催化反应中研究者观察到一个反应速率始终为零的特殊阶段，在这个阶段之后反应自发开始。这两种阶段形成的原因与反应的机理尤其是催化剂的活化和失活有关。然而，这两个具有明显不同特征的阶段往往被混淆。本文通过所选取的一些代表性的催化反应分别介绍了"诱导期"和"休眠期"的动力学特征，讨论了两者之间的区别。期待这些隐藏在稳态催化循环之前的阶段能够得到更多的关注，这将有利于研究人员深度理解有机化学反应中的前催化循环和详细的反应机理。     

Palladium-catalyzed cross-coupling reactions of coumarin derivatives: An overview

Coumarins are omnipresent in several plants and exhibit a plethora of pharmacological properties, making them an important scaffold in organic synthesis. Naturally, the chemistry of this motif has attracted ever-increasing attention, among which palladium-catalyzed coupling reactions are the most prevalent one. Numerous useful, easy, and concise syntheses and reactions have been achieved using palladium-catalyzed coupling reactions. This review focuses on recent advances in palladium-catalyzed cross-coupling reactions such as Suzuki, Heck, Stille, Sonogoshira etc. reactions of coumarin derivatives and covers the literature from 2001 to 2020.     

Transformations based on ring-opening of gem-difluorocyclopropanes

gem-Difluorocyclopropanes are an important fluorinated class of compounds with applications in medicinal chemistry, material sciences and organic synthesis. The transformations based on their ring-opening reactions have been recognized to be useful methods for rapidly synthesizing various fluorinated organic molecules. In this digest paper, we describe these efforts and highlight their powerfully potential and applications as fluorine-containing synthons in organic chemistry.     

Effect of polymer as cosolvent on chemical reactions in solution—I. Effects of polystyrene and polyoxyethylene on the reaction of dansyl chloride with butylamine in organic solvents

The rates of reactions of 5-dimethylamino-1-naphthalenesulphonyl chloride (dansyl chloride) with butylamine in organic solvents have been measured in the presence of polymer such as polyoxyethylene (POE) or polystyrene (PS) as cosolvent and compared with those in the presence of cosolvents of low molecular weight analogues, viz. diethyloxyethane (DEE) and toluene (Tol.). Acceleration by cosolvent POE, compared with DEE, increases with increasing volume fraction of cosolvent and the effect depends on the degree of polymerization of the polymer cosolvent. Similarly, addition of cosolvent PS to ethyl acetate or chloroform results in increase in the reaction rate as compared with cosolvent Tol. The effect by PS also showed dependence on the degree of polymerization. The effect of polymer cosolvent on chemical reactions between two low molecular weight species is explained in terms of the thermodynamics of polymer solutions.     

Application of N-halo reagents in organic synthesis

This review article summarizes published data on the application of N-halo reagents (such as N-halo amines, N-halo amides and/or imides, N-halo sulfonamides and/or imides, and etc.) in various organic functional group transformations such as: oxidation reactions, deprotection and protection of different functional groups, halogenation of saturated and unsaturated compounds, acylation of alcohols, phenols, amines or thiols, epoxidation of alkenes, aziridination and etc. The main purpose of writing this review is encouraging of active researchers interested to this field for the synthesis of new N-halo reagents specially with different halogens and applications of these new N-halo reagents in organic reactions or finding more and more applications of existing N-halo reagents in organic synthesis.     

Interfacial energy exchange and reaction dynamics in collisions of gases on model organic surfaces

Molecular beam scattering experiments and molecular dynamics simulations have been combined to develop an atomic-level understanding of energy transfer, accommodation, and reactions during collisions between gases and model organic surfaces. The work highlighted in this progress report has been motivated by the scientific importance of understanding fundamental interfacial chemical reactions and the relevance of reactions on organic surfaces to many areas of environmental chemistry. The experimental investigations have been accomplished by molecular beam scattering from ω-functionalized self-assembled monolayers (SAMs) on gold. Molecular beams provide a source of reactant molecules with precisely characterized collision energy and flux; SAMs afford control over the order, structure, and chemical nature of the surface. The details of molecular motion that affect energy exchange and scattering have been elucidated through classical-trajectory simulations of the experimental data using potential energy surfaces derived from ab initio calculations. Our investigations began by employing rare-gas scattering to explore how alkanethiol chain length and packing density, terminal group relative mass, orientation, and chemical functionality influence energy transfer and accommodation at organic surfaces. Subsequent studies of small molecule scattering dynamics provided insight into the influence of internal energy, molecular orientation, and gas–surface attractive forces in interfacial energy exchange. Building on the understanding of scattering dynamics in non-reactive systems, our work has recently explored the reaction probabilities and mechanisms for O₃ and atomic fluorine in collisions with a variety of functionalized SAM surfaces. Together, this body of work has helped construct a more comprehensive understanding of reaction dynamics at organic surfaces.     

Selective chemical reactions in supercritical carbon dioxide,water, and ionic liquids

Abstract

Alternative solvents such as supercritical carbon dioxide, water, and ionic liquids are receiving an increase of interest as better replacements for conventional solvents in chemical reactions. They have been called sustainable green solvents because they are highly promising reaction mediums for organic synthesis. This review presents an overview of some selected chemical reactions that have been developed in these green solvents with a particular emphasis on metal-catalyzed reactions.     

离子液体在氟化反应中的应用进展

离子液体作为一类新型绿色溶剂,具有制备简单、稳定性好、溶解能力强、挥发性小、安全性强等优点,因此在有机单元反应包括酯化、氧化、还原、重排反应等中的应用相当广泛,有着十分诱人的应用前景.虽然其在氟化反应中的应用研究开始得较晚,但发展很快,目前在重氮化氟化、亲核氟化、亲电氟化以及电化学氟化等方面都取得了较大的进展.本文综述了近年来离子液体在氟化反应中应用的最新进展情况,并对其未来发展方向和应用前景进行了展望.