Photochemical C–N bond forming reactions for the synthesis of five-membered fused N-heterocycles

Abstract

Few conversions cannot take place with ground-state reactions even with the help of a catalyst, therefore they are made to occur under photochemical conditions. The transfer of electrons took place even with the photochemical excitement of one molecule where redox reaction cannot occur at the ground state. The ground-state reactions resulted in the formation of side products. The substrates did not require any sort of chemical activation for C–N bond construction in the course of photochemical reactions. The source of energy; light has always been the interest of researchers in order to induce chemical reactions ever since the starting of scientific chemistry. The present review encloses the chemistry of photochemical transformations with a focus on their synthetic uses. The organic photochemical reactions prevent the polluting or harmful reagents thus, provides a possibility for sustainable procedures as well as green chemistry. This review article displays the formation of numerous of five-membered fused nitrogen-heterocyclic compounds.     

Chemistry of bicyclic 5-6 systems: Synthesis of oxazolo[3,2-a]pyridines and their salts with a ring-junction nitrogen atom

The present review highlights the synthetic procedures reported for the preparation of oxazolo[3,2-a]pyridines as a class of 5-6 bicyclic heterocycles with a nitrogen atom at the ring junction. The different sections included the synthesis of the investigated analogs through the reactions of (1) β-ketoesters with α,β-unsaturated ketones (2) δ-oxoacids or esters or unsaturated carboxylic acids with glycinol derivatives (3) unsaturated ketoesters with enamines (4) ethoxymethylenes with amidoglycinol derivatives (5) pyridinium salts with phenylglycinol (6) Multicomponent reactions, and (7) Synthesis of tetracyclic systems. The aim of the present study is to demonstrate a synopsis of the synthesis of compounds containing oxazolo[3,2-a]pyridine skeleton with high yields using readily and accessible starting materials, and efficient synthetic routes until now. The stereochemistry of the obtained enantiopure heterocycles, the isolation of the isomers and the reaction mechanisms of the unexpected products are discussed.     

A Mild and Efficient Route to 3-Vinylchromones in Aqueous Micellar Media

A simple, mild, and ecofriendly method has been developed for the synthesis of 3-vinylchromones from 4-oxo-4H-1-benzopyran-3-carboxaldehyde (3-formylchromone) by simple Knoevenagel condensation with various active methylene compounds (AMC) in aqueous micellar media in the presence of catalytic amounts of cetyl trimethylammonium bromide (CTAB) and 1,4-diazabicyclo[2.2.2]octane (DABCO). In the case of malonic acid as AMC, the reaction resulted in formation of only Doebner decarboxylated products under the standard reaction condition. It has been also observed that 3-formylchromone derivatives primarily undergo tandem Knoevenagel and Michael reactions in the presence of > 2 equiv. of ethyl acetoacetate to produce benzophenone derivatives, by opening of pyran ring, as the sole product in good yields.     

The Forgotten Carbonyl Reaction: Chloroacetylation and Bromoacetylation of Carbonyl Compounds

Halomethyl acetates ( 3 ) could be prepared from aliphatic, α,β‐unsaturated and aromatic aldehydes, as well as from alicyclic ketones with high yields in simple one‐pot reactions. Very often, the products didn't have to be purified and could directly be used for synthetic purposes after evaporation of the solvent. Obviously, the ‘bad reputation’ of the reaction in the literature stemed from the fact that the reactions didn't take place under the best conditions. Carbonyl compounds ( 1 ) and acyl halides ( 2 ) form equilibria which are completely on the side of the halomethyl acetates ( 3 ) at room temperature (starting with aliphatic and most aromatic aldehydes) and which can be strongly influenced by the reaction parameters. It is crucial to work at low temperature in apolar solvents and to remove (or deactivate) the catalyst before workup. Reactions may be realized with or without solvents. Side reactions were observed with formaldehyde and acetaldehyde but, with exception of formaldehyde, could be reduced close to zero (see Fig. 5). By‐products were essentially avoided if the reaction took place in apolar solvents and with a local excess of acetyl chloride. In many cases clean products were available which could directly be used for synthetic purposes. Halomethyl acetates ( 3 ) are bifunctional carbonyl derivatives with two different leaving groups, whose preparative advantages have been useful for the synthesis of various pentafulvenes, but were especially important for preparing unstable parent fulvenes and fulvalenes.     

Indole‐N‐Carboxylic Acids and Indole‐N‐Carboxamides in Organic Synthesis

Indoles are ubiquitous structures that are found in natural products and biologically active molecules. The synthesis of indoles and indole‐involved synthetic methodologies in organic chemistry have been receiving considerable attention. Indole‐N‐carboxylic acids and derived indole‐N‐carboxamides are intriguing compounds, which have been widely used in organic synthesis, especially in multicomponent reactions and C?H functionalization of indoles. This Minireview summarizes the advances of reactions involving indole‐N‐carboxylic acids and indole‐N‐carboxamides in organic chemistry, and discusses the synthetic potential and perspective of this field.     

Fluorinated 1,2,4-triketone analogs: new prospects for heterocyclic and coordination chemistry

The review is focused on the synthetic approaches to polyfluoroalkylated acetal-functionalized β-diketones and their cyclic derivatives (furan-3(2H)-ones and chromones) as analogs of 1,2,4-triketone. The synthetic possibilities of these compounds for construction of heterocycles and coordination compounds are considered.

     

Chemistry of Pentafluorosulfanyl Derivatives and Related Analogs: From Synthesis to Applications

Pentafluorosulfanyl (SF₅)-containing compounds and corresponding analogs are a highly valuable class of fluorine-containing building blocks owing to their unique properties. The reason for that is the set of peculiar and tremendously beneficial characteristics they can impart on molecules once introduced onto them. Despite this, their application in distinct scientific fields remains modest, given the extremely harsh reaction conditions needed to access such compounds. The recent synthetic approaches via S−F, and C−SF₅ bond formation as well as the use of SF₅-containing building blocks embody a “stairway-to-heaven” loophole in the synthesis of otherwise-inaccessible chemical scaffolds only a few years ago. Herein, we report and evaluate the properties of the SF₅ group and analogs, by summarizing synthetic methodologies available to access them as well as following applications in material science and medicinal chemistry since 2015.     

THE INVESTIGATION OF MONOMER SYNTHESIS METHODS FOR POLYSULFONES AND OTHER NEW CLASSES OF SULFUR-CONTAINING POLYMERS

Abstract

Polysulfones, the new promising class of sulfur-containing polymers, are produced by aromatic nucleophilic and electrophilic substitution reactions. The first way is based on 4,4′-dichlorodiphenylsulfone (DCDPS) application as one of the basic monomers, which can be produced by three technical methods, utilizing strong sulfonating and sulfonylating agents. The reaction of hydrocarbon sulfonylation with arylsulfochlorides in the presence of small quantities of Fe chloride (kinetics, mechanism, the reactivity of initial compounds) was investigated in detail. For the first time the competitive inhibiting by initial and final products was found in this reaction, and its quantitative evaluation was given. The data obtained allowed to explain the experimentally observed anomalous reactivity of arylsulfochlorides. The chemistry of sulfonylation reaction with stabilized liquid sulfuric anhydride and dimethylsulfate was thoroughly investigated. The peculiarities and application limits of substituted diphenylsulfones synthesis methods were discussed.     

资源化学研究进展*

本文总结了本课题组在资源化学领域的研究工作进展,内容涉及到天然资源化合物甾体皂甙元和非天然资源性化合物氟烷基磺酰氟的反应及其在有机合成中的应用。首先介绍了原子经济性地利用甾体皂甙元资源的策略与方法。为解决甾体皂甙元资源在工业利用过程产生的环境污染和资源浪费问题,我们发展了用30%双氧水代替铬酐氧化降解假甾体皂甙元的方法,使“百分之百”利用甾体皂甙元资源的理想成为现实。双氧水与乙酸原地产生的过氧酸直接氧化甾体皂甙元成为孕甾-16,20-二醇类化合物和4R-甲基-5羟基戊酸内酯,通过甾体皂甙元的非正常Baeyer-Villiger反应合成了甾体-16羟基-22-内酯类化合物和3R-甲基-5羟基戊酸内酯。所获甾体中间体和带甲基侧链的双官能团手性试剂被应用于部分甾体药物、昆虫信息素、香料和天然产物的合成中。另外还介绍了利用甾体皂甙元完整骨架合成目标分子的资源性化合物利用策略。本文第二部分内容介绍了氟烷基磺酰氟资源利用的策略和方式。反应共生是我们提高氟烷基磺酰氟资源利用率的新思路,基于共生反应概念,研究了邻二醇环氧化反应、烯烃环氧化反应和碳正离子重排等反应与氟烷基磺酰氟水解反应的共生反应,并且介绍了其合成应用实例。     

Review Article: Anionic Conjugate Addition Reactions for the Preparation of Substituted Monosaccharides and Disaccharides

1. INTRODUCTION

Conjugate addition reactions are widely used synthetic tools in general organic chemistry,¹ and starting in the early 1960s they were introduced into carbohydrate chemistry. Since then a considerable number of publications have described the utilisation of different types of conjugate addition reactions in the field of carbohydrate chemistry but to date this area has not been reviewed.     

Synergistic Catalysis with Azomethine Ylides

Azomethine ylides are useful intermediates for the rapid construction of chiral N‐containing compounds. However, its synthetic potential has not been fully developed due to the limited reaction models. In combination with synergistic catalysis and azomethine ylide chemistry, we have developed several types of novel catalytic system including Cu/Pd, Cu/Ir and PTC/Ir catalysis, which can convert readily‐available azomethine ylides to various high‐valued molecules such as unnatural α‐amino acids, homoallylic amines and N‐heterocycles. Compared with the traditional mono‐catalysis, the synergistic catalyst system exhibits enhanced catalytic efficiency and chiral induction ability in many cases. In addition, we have demonstrated that these strategies could be applied in the construction of bioactive compounds and natural products.     

Greening the organic chemistry laboratory: a comparison of microwave-assisted and classical nucleophilic aromatic substitution reactions

ABSTRACT

An experiment is described for the undergraduate organic chemistry lab which compares microwave-induced organic reaction enhancement (MORE) to that of more traditional synthetic procedures. MORE and traditional reflux procedures for substituting thiocyanate, ethylamine and diethylamine nucleophiles for bromide in nucleophilic aromatic substitution reactions on 1-bromo-2,4-dinitrobenzene are given. Recrystallization affords products of sufficient purity for characterization by ¹³C NMR, mass spectrometry and melting point. As students compare the two synthetic methods, MORE procedures are consistently observed to be quicker, easier, greener and result in higher yields. Student instructions, instructor notes and example NMR and mass spectra obtained by students are provided in Supplemental material.     

Unsaturated Sugars : An Alternative Route to 3, 5, 6-Trideoxy-1, 2-O-Isopropylidene-α-D-Glycero-Hex-3, 5-Dienofuranose

Unsaturated sugars are among the most important and useful compounds in carbohydrate chemistry. They assume key roles in the synthesis of modified sugars and complex natural products. The title compound 5, an unsaturated sugar containing a conjugated diene system, has been reported¹ recently and its potential synthetic value for Diels-Alder reaction giving access to functionalized annulated furanoses has been pointed out.² For a different synthetic purpose we prepared this compound by an alternative route albeit from the same starting material used by the previous authors. Our synthetic sequence is outlined in the following scheme.     

The synthesis of N-containing heterocyclic compounds catalyzed by copper/L-proline

N-containing heterocyclic compounds are one of the most important motifs prevalent in various bioactive natural products and pharmaceuticals. Given the significance of N-containing heterocyclic compounds, various synthetic strategies have been developed. Copper/ligand (abbreviated as [CuL])-catalyzed cascade reaction is a powerful and efficient tool for the construction of N-containing heterocyclic compounds. L-proline is one universal ligand and has been utilized in the copper-catalyzed reactions. In this review, copper/L-proline-catalyzed tandem reaction to synthesize the five- and six-membered compounds is emphatically introduced. By comparing the yields in the presence and absence of the ligand, the importance of L-proline is recorded. Moreover, the function of L-proline is expounded on the basis of the reaction mechanism from original article.     

STUDIES IN THE HETEROCYCLIC SERIES. IX. SYNTHESIS OF HETEROCYCLIC THIOLS

Abstract

A survey of the chemical literature recently undertaken by us, has revealed that much greater attention is being given nowadays to organo-sulfur compounds. New products containing sulfur have emerged and many of them were isolated from coal, 3 plant, animals' and soil microbes. 6 A great majority of them are, however, man-made and are obtained by intricate but often exciting synthetic procedures which give rise to new reactions, new chemistry and a great variety of potentially useful chemical compounds. These studies led to the synthesis of derivatives of phenothiazine (1)7 the sulfur analog of phenoxazine, and to dithieno(2,3-b: 2′,3′-e)(l,4)thiazine (2)′, cyclopental(1,2-b: 4,3-bf)-dithiophene (3)9 and benzothienoacridine (4) derivatives which are thiophene analogs of phenothiazine, fluorene and benz(c)acridine respectively.     

Synthetic strategies and functional reactivity of versatile thiophene synthons

Abstract

Thiophenes are a highly important group of heterocycles and have been of great interest to researchers due to their various reactivities. Many synthetic strategies are used to generate functionalized thiophene derivatives. Several reactions are described, depending on the reactivity of the substituents attached to the thiophene nucleus toward different nucleophiles to yield the versatile thiophene products. Many diverse applications have been utilized for thiophenes from medicinal chemistry to material science.     

Reissert compounds and their open-chain analogs in organic synthesis

Reactions of major synthetic interest employing Reissert compounds (1, 2-dihydro-1-acyl-2-cyanoquinolines and 1, 2-dihydro-2-aqyl-1-cyanoisoquinolines) and related heterocyclic species are surveyed. The chemistry of open-chain analogs of Reissert compounds (i.e., derivatives of N-acyl-α-aminoacetonitriles) is described and compared with conventional Reissert compounds.     

Chemistry of antipyrine

This review is a literature survey of antipyrine, considered as one of the most valuable compounds in the fields of organic and medicinal chemistry. The biological importance, synthetic procedures, and reactions are discussed. Generally, the preparation of antipyrine was reported through the methylation of the corresponding 1H-pyrazolone following different reaction conditions. The reactions, in general, are electrophilic substitutions at C₄-position of pyrazolone. The mechanistic pathways of the reactions are surveyed.     

Untersuchungen der Reaktionsprodukte von Isocyanaten mit Hydroxylamin

Investigations of the Products of Isocyanates with Hydroxylamine The reactions of isocyanates with hydroxylamine give rise to several compounds according to the different conditions involved when starting with the primary reaction products, the hydroxy-ureas. The pure compounds have been isolated. An interesting reaction of N-phenyl-N′-phenylcarbamoyloxyurea with sodium hydroxide has been observed. This compound is converted to 3-hydroxy-1, 5-diphenylbiuret under conditions described.