Synthesis Of Five-membered Heterocycles Research Articles

Recent Advances in Design and Synthesis of 1,3-Thiaselenolane and 1,3-Thiaselenole Derivatives

Recent advances in the design and synthesis of five-membered heterocycles containing both sulfur and selenium atoms—1,3-thiaselenolane and 1,3-thiaselenole derivatives—are discussed in this review. These heterocyclic systems are of interest as intermediates for organic synthesis and compounds that can exhibit various useful properties, including biological activity and electrical conductivity. The main focus of the review is on the works of the last 20 years that make use of catalytic reactions. Synthetic methods for the preparation of structurally related 1,4,5,8-diselenadithiafulvalenes based on catalytic cross-coupling reactions are also presented. To date, the design and synthesis of 1,3-thiaselenolane and 1,3-thiaselenole derivatives have not been discussed in a separate review.

Synthesis of five-membered heterocycles by [3+2] cycloaddition reactions of sulfur-containing 3,3,3-trifluoropropene derivatives

Synthesis of five-membered heterocycles by [3+2] cycloaddition reactions of sulfur-containing 3,3,3-trifluoropropene derivatives

Synthesis of Five-Membered Heterocycles by H3PO2-Catalyzed Cyclization of Stereodefined Alcohols

Synthesis of Five-Membered Heterocycles by H3PO2-Catalyzed Cyclization of Stereodefined Alcohols

THE USE OF N -HALOSUCCINIMIDES FOR CYCLIZATION WITH THE FORMATION OF FIVE-MEMBERED HETEROCYCLIC COMPOUNDS

The review summarizes the literature data for the period 2000–2017 on the most successful use of N -halosuccinimides in the preparative synthesis of five-membered heterocyclic compounds. The review is structured in accordance with the classification of the synthesized heterocycles with one (furans, thiophenes, selenophenes, pyrroles, and their analogs), two (oxazoles, isoxazoles, thiazoles, isothiazoles, pyrazoles, imidazoles), three (oxadiazoles, triazoles), or four heteroatoms (tetrazoles). The bibliography of the review includes 117 references to literary sources.

The use of N-halosuccinimides for cyclization with the formation of five-membered heterocyclic compounds

The review summarizes the literature data for the period 2000–2017 on the most successful use of N-halosuccinimides in the preparative synthesis of five-membered heterocyclic compounds. The review is structured in accordance with the classification of the synthesized heterocycles with one (furans, thiophenes, selenophenes, pyrroles, and their analogs), two (oxazoles, isoxazoles, thiazoles, isothiazoles, pyrazoles, imidazoles), three (oxadiazoles, triazoles), or four heteroatoms (tetrazoles). The bibliography of the review includes 117 references to literary sources.

Synthesis of Five-Membered Heterocycles Containing Nitrogen Heteroatom Under Ultrasonic Irradiation

Ultrasonic irradiation is employed to accelerate organic reactions. Under sonication reduced time, good selectivity, excellent yield, and milder conditions were observed for many organic reactions. Ultrasonic reactions are increasingly used as green, clean, and environment-friendly methods in organic synthesis in terms of energy conservation and waste minimization. The use of ultrasound irradiation is increasing in coming years. The use of ultrasound irradiation in the synthesis of five-membered N-heterocycles is depicted in the present review article.

Synthesis of Five-Membered Heterocycles Starting from Cyclopropanes

Synthesis of Five-Membered Heterocycles Starting from Cyclopropanes

Catalytic Annulation of Epoxides with Heterocumulenes by the Indium-Tin System.

In the synthesis of five-membered heterocycles by the annulation of epoxides with heterocumulenes such as carbon dioxide and isocyanates, we developed the indium-tin catalytic system and synthesized various cyclic adducts including novel types products under mild reaction conditions.

ChemInform Abstract: Synthesis of Five‐Membered N,N,N‐ and N,N,N,N‐Heterocyclic Compounds: Applications of Microwaves

AbstractReview: 111 refs.

ChemInform Abstract: Environmentally Benign Synthesis of Five‐Membered 1,3‐N,N‐Heterocycles by Microwave Irradiation

AbstractReview: 121 refs.

Synthesis of Five-Membered Heterocycles by Indirect Electrochemical Approach in “Green” Media

Radical cyclization continues to be a central methodology for the preparation of natural products containing heterocyclic rings. Hence, some electrochemical results obtained by cyclic voltammetry and controlled-potential electrolysis in the study of electroreductive intramolecular cyclization of ethyl (2S, 3R)-2-bromo-3-propargyloxy-3-(2′,3′,4′,6′-tetra-O-acetyl-β-D-glucopyranosyloxy) propanoate (1a), 2-bromo-3-allyloxy-3-(2′,3′,4′,6′-tetra-O-acetyl-β-D-glucopyranosyloxy)propanoate (1b), 2-bromo-[1-(prop-2-yn-1-yloxy)propyl]benzene (1c) and [1-bromo-2-methoxy-2-(prop-2′-yn-1-yloxy)ethyl]benzene (1d) promoted by (1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane)nickel(I), [Ni(tmc)]+, electrogenerated at glassy carbon cathodes in ethanol and ethanol:water mixtures containing tetraalkylammonium salts, are presented. During controlled-potential electrolyses of solutions containing [Ni(tmc)]2+ and bromoalkoxylated compounds (1) catalytic reduction of the latter proceeds via one-electron cleavage of the carbon–bromine bond to form a radical intermediate that undergoes cyclization to afford the substituted tetrahydrofurans.

ChemInform Abstract: Aziridines in Formal [3 + 2] Cycloadditions: Synthesis of Five‐Membered Heterocycles

AbstractReview: 64 refs.

Copper-Catalyzed Synthesis of N-Heterocyclic Compounds

The synthesis of N-heterocyclic compounds is an important direction because of their diverse biological functions. Recently, there has been remarkable progress in copper-catalyzed cross couplings with inexpensive, readily available, insensitive-to-air and low-toxicity copper catalysts. This review summarizes recent advances in the copper-catalyzed synthesis of N-heterocyclic compounds. 1 Introduction and Background 2 Synthesis of Five-Membered Heterocycles with One Nitrogen Atom 2.1 Pyrrolidine and Pyrrole Derivatives 2.2 Indole Derivatives 2.3 Indolone and Isoindolone Derivatives 2.4 Oxazole, Isoxazole, Benzoxazole and Benzothiazole Derivatives 3 Synthesis of Five-Membered Heterocycles with Two Nitrogen Atoms 3.1 Imidazole Derivatives 3.2 Benzimidazole Derivatives 3.3 Benzimidazolone Derivatives 4 Synthesis of N-Sulfonyltriazoles 5 Synthesis of Six-Membered Heterocycles with One Nitrogen Atom 5.1 Piperidine and Pyridine Derivatives 5.2 Quinoline and Quinolinone Derivatives 5.3 Isoquinoline Derivatives 6 Synthesis of Six-Membered Heterocycles with Two Nitrogen Atoms 6.1 Quinazoline Derivatives 6.2 Quinazolinone Derivatives 7 Synthesis of N-Fused Heterocycles 8 Summary

Recent Advances in the Synthesis of Five-Membered Heterocycles

Five-membered heterocycles are very important from the synthetic aspect because of their enormous pharmacological applications. Several new reagents, substrates and methods are being developed every year to facilitate their synthesis. This review is an effort to sum up the methods recently utilized in the synthesis of this important group of heterocycles. Keywords: Azole, oxadiazole, thiadiazole, triazole, selenazole, furan

Palladium-Catalyzed Synthesis of Five-Membered Heterocycles from 1,6-Enynes

Palladium-Catalyzed Synthesis of Five-Membered Heterocycles from 1,6-Enynes

Reactivity of Arylnitrile Oxides and C-Aroyl-N-phenylnitrones with 3-Methylenedihydro-(3H)-furan-2-one and Itaconic Anhydride

1,3-dipolar cycloaddition is a powerful route for the synthesis of five-membered heterocycles. The [3+2] cycloadditions of some alpha-methylene-gamma-buryrolactones, namely 3-methylenedihydro-(3H)-furan-2-one (1) and itaconic anhydride (2) were Studied. Their reactions with arylnitrile oxides (3) and Caroyl-N-phenylnitrones (7) proceed with complete regioselectivity. From a stereochemical point of view, the addition of arylnitrile oxides (3) leads to the unique spiroheterocycles (4-5). Actually, a single stereocenter is generated during the reaction. In the particular case of p-nitrophenylnitrile oxide (3d), only the diacidic form (10d) of the spiroheterocyle (5d) was isolated. In contrast, the addition of C-aroyl-N-phenylnitrones (7) produces a couple of diastereoisomers. since two stereocenters are generated simultaneously. Nevertheless, the reaction is regioselective and stereospecific leading also to the single spiroheterocycles (1920). The proposed stereochemistry of spiranic compounds (19d) and (20d) has been corroborated by two single crystal X-ray crystallographic analysis.

Ylide-Initiated Michael Addition−Cyclization Reactions beyond Cyclopropanes

[Reaction: see text]. Ylides are nucleophiles that bear a unique leaving group, L n M, and can attack aldehydes, ketones, imines, and electron-deficient alkenes. Over the course of the reaction, they react with CX (X = C, N, O, etc.) double bonds to form betaine or oxetane intermediates, which further eliminate the heteroatom-containing group in one of two ways to give the corresponding olefination or cyclization product. Since the discovery of the Wittig reaction, ylide olefination has developed as one of the most useful approaches in constructing carbon-carbon double bonds. These reactions provide unambiguous positioning of the C-C double bond and good stereoselectivity. Researchers have also widely used ylides for the synthesis of small ring compounds such as epoxides, cyclopropanes, and aziridines. However, the use of ylides to prepare larger cyclic structures was very limited. This Account outlines our recent work on ylide-initiated Michael addition/cyclization reactions. By altering the heteroatoms and the ligands of the ylides, we have modulated the reactivity of ylides. These modified ylides provide easy access to diverse cyclic compounds with the ability to control regioselectivity, chemoselectivity, diastereoselectivity, and enantioselectivity. Reactions using these ylides produce the structural components of many biologically active compounds and valuable intermediates in organic synthesis. Allylic telluronium and sulfonium ylides can react with alpha,beta-unsaturated esters, ketones, amides, and nitriles to afford multisubstituted vinylcyclopropanes with high selectivities. Telluronium allylides react with aromatic N-phenyl aldimines to give trans-vinylaziridines and with chiral N- tert-butylsulfinylimines to afford the optically active cis-2-substituted vinylaziridines, both with high diastereoselectivities. We also used sulfonium and telluronium allylides to prepare vinylepoxides. In addition, ylides are good reagents for the synthesis of five-membered heterocyclic compounds. By treatment of stable camphor-derived sulfur ylides with alpha-ylidene-beta-diketones, we obtained multisubstituted dihydrofurans with high diastereo- and enantioselectivities. Ammonium salts derived from cinchonidine and cinchonine react smoothly with 3-aryl and 3-heteroaryl-2-nitro acrylates, affording both enantiomers of isoxazoline N-oxides with up to 99% ee. Ylides can initiate tandem cyclizations for the synthesis of chromenes, bicyclic compounds, and cyclohexadiene epoxides. Varying the choice of base allows access to 2 H-chromenes and 4 H-chromenes from 3-(2-(bromomethyl)phenoxy)acrylates via a tandem ylide Michael addition/elimination/substitution reaction. Phosphines can catalyze an intramolecular ylide [3 + 2] annulation constructing bicyclo[ n.3.0] ring systems with three contiguous stereogenic centers. The reaction of crotonate-derived sulfur ylides with alpha,beta-unsaturated ketones affords cyclohexadiene epoxides with excellent diastereoselectivities (>99/1) in good to high yields. Using a camphor-derived sulfonium salt, we have produced asymmetric cyclohexadiene epoxides with high ee's. Overall, these results illustrate the versatility and tunability of ylides for the preparation of cyclic systems containing more than three atoms.

Multicomponent Reactions of Carbonyl Compounds and Derivatives of Cyanoacetic Acid: Synthesis of Carbo- and Heterocycles

We present herein a review of multicomponent reactions of carbonyl compounds with derivatives of cyanoacetic acid, and denote their differences from other well-known multicomponent reactions. Although this class of multicomponent reactions is widely used in organic chemistry for the synthesis of carbo- and heterocycles, it has not yet been reviewed in a separate publication. This review includes available information on the synthesis of carbocycles (substituted cyclopropanes, spiro-conjugated cyclopropanes, five- and six-membered carbocycles), five-membered heterocycles (furans, thiophenes, pyrroles, thiazoles, and others), and six-membered heterocycles (pyrans, thiopyrans, and pyridines) using the multicomponent reaction of carbonyl compounds with derivatives of cyanoacetic acid. 1 Introduction 2 Multicomponent Carbocyclic Synthesis 2.1 Synthesis of Cyclopropanes 2.2 Synthesis of Five- and Six-Membered Carbocycles 3 Multicomponent Heterocyclic Synthesis 3.1 Synthesis of Five-Membered Heterocycles 3.2 Synthesis of Six-Membered Heterocycles 4 Conclusion

Comment on the Electronic Reorganization in 1,3-Dipolar Cycloaddition of Fulminic Acid to Acetylene

Department of Chemistry, UniVersity of LeuVen,Celestijnenlaan 200F, B-3001 LeuVen, Belgium, NationalInstitute of AdVanced Industrial Science and Technology,AIST Tsukuba Central 5, Tsukuba 305-8565, Japan, andDepartment of Information Systems Engineering, Faculty ofEngineering, Osaka Sangyo UniVersity, Daito 574, JapanReceiVed: January 23, 2001; In Final Form: July 5, 2001In this note, we comment on the electronic mechanism ofthe concerted 1,3-dipolar cycloaddition reaction of fulminic acidto acetylene (HCNO + HCCH), which has recently been studiedby valence bond and molecular orbital approaches by fourdifferent groups including ourselves: (i) Sakata, K. J. Phys.Chem. A 2000, 104, 10001, (ii) Harcourt, R. D.; Schulz, A. J.Phys. Chem. A 2000, 104, 6510, (iii) Nguyen, M. T.; Chandra,A. K.; Sakai, S.; Morokuma, K. J. Org. Chem. 1999, 64, 65,and (iv) Karadakov, P. B.; Cooper, D. L.; Gerratt, J. Theor.Chem. Acc. 1998, 100, 222. The main discrepancy arising fromthese theoretical studies concerns the electronic reorganization,and in particular, the direction of the electron flow accompany-ing the nuclear deformation at the transition structure. Wepresent additional results supporting our earlier findings that inthe 1,3-dipolar cycloaddition of fulminic acid (HCNO) andprobably substituted nitrile-oxides (RCNO), to alkynes andphosphaalkynes, the oxygen (O) atom behaves as a bondacceptor center and the carbon (C) as a bond donor.The 1,3-dipolar cycloaddition is a general and powerfulmethod for the synthesis of five-membered heterocyclic com-pounds owing to the great variety and availability of dipolesand dipolarophiles.

ChemInform Abstract: Synthesis of Five-Membered Heterocycles from Novel Functionalized Allenes

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.