Dinucleophilic Reagents Research Articles

Carbonyl-Assisted Iridium-Catalyzed C-H Amination Using 2,2,2-Trichloroethoxycarbonyl Azide.

The carbonyl-directed, mono C-H amination of arenes has been achieved using [Cp*Ir(III)Cl2]2 as the catalyst and 2,2,2-trichloroethoxycarbonyl (Troc) azide as an aminating reagent. The amination proceeds smoothly with a variety of arylcarbonyl compounds, including alkyl and vinyl arylketones, secondary and tertiary aryl amides, and acetyl indoles. The resulting ortho-TrocNH arylcarbonyl compounds are easily transformed to the corresponding free arylamines, aryl carbamates, or aryl ureas. Taking advantage of the electrophilic nature of both Troc and carbonyl groups in ortho-TrocNH arylcarbonyl compounds, the subsequent cyclization with dinucleophilic reagents has also been demonstrated. This provides an efficient strategy for the construction of aryl-fused N-heterocycles.

Recent Advances in C-C/Heteroatom Bond Forming and Annulation Reactions of β- Ketodithioesters.

β-Ketodithioesters (KDEs) are versatile building blocks for the rapid construction of various heterocyclic compounds. Quite a good number of successful reactions based on KDEs have been developed in the past decade for the construction of heterocyclic skeletons under mild conditions. This review covers the new CC/ X bond formation and annulation reactions of KDEs with dielectrophilic or dinucleophilic reagents. Multicomponent reactions using KDEs to construct various heterocycles are also the major contents in this review. Objective: The aim of this review is to bring a fresh perspective on the application of KDEs in organic synthesis covering from 2013 to 2020. Conclusion: From this review, it has been cleared that KDEs have been the object of numerous studies on its use in heterocyclic synthesis. The presence of different functional groups on this synthon permits the incorporation of C-C/X sources into the final targets, which is the significant property of KDEs.

Synthesis and Antimicrobial Activity of 3-Phenyl-1-Methylquinolin-2-One Derivatives

A series of quaternary salts were obtained by reacting 3-(4-bromoacetylphenyl)-1-methylquinolin-2(1H)-one with Py, 4-methylpyridine, quinoline, benzo[f]quinoline, and triphenylphosphine. Derivatives of thiazole, imidazo[1,2-a]pyridine, and imidazo[1,2-a]pyrimidine were produced using dinucleophilic reagents. Several of the synthesized compounds possessed high antimicrobial activity, indicating that further research on this series of compounds was promising.

Palladium‐Catalyzed Acylation Reactions: A One‐Pot Diversified Synthesis of Phthalazines, Phthalazinones and Benzoxazinones

A sequential one‐pot strategy for the diversified synthesis of phthalazines, phthalazinones and benzoxazinones was presented. This strategy proceeds through [Pd]‐catalyzed acylation and nucleophilic cyclocondensation with dinucleophilic reagents. This process was based on direct coupling with simple bench‐top aldehydes without the assistance of directing group and without activating the carbonyl group. The process is highly advantageous because it employs simple nitrogen‐based nucleophiles, and non‐toxic and readily accessible aldehydes as the carbonyl source. Most importantly, the strategy was applied to the one‐pot synthesis of PDE‐4 inhibitor.

ChemInform Abstract: β‐Ketothioamides: Efficient Reagents in the Synthesis of Heterocycles

AbstractReview: [37 refs.

ChemInform Abstract: The Use of 2‐(1‐Alkoxyalkylidene)‐1,3‐dicarbonyl Compounds in Organic Synthesis.

The review focuses on the methods of synthesis of 2-(1-alkoxyalkylidene)-1,3-dicarbonyl compounds and their chemical transformations. The reactivity of such compounds toward various mono- and dinucleophilic reagents is considered. The potential of these compounds for synthesis of different acyclic, carbo- and heterocyclic molecules is demonstrated. Special attention is paid to the practical use of 2-(1-alkoxyalkylidene)-1,3-dicarbonyl compounds and their derivatives, which are of interest in medicine and for design of new materials. The bibliography includes 226 references.

ChemInform Abstract: The First Example of 3,7‐Diazabicyclo[3.3.1]nonane Synthesis by Aminomethylation of Guareschi Imide Salts.

2,6-Dioxopiperidine-3,5-dicarbonitriles (also known as Guareschi imides) and their salts are readily prepared by condensation of ketones, cyanoacetic ester, and ammonia [1-3] and have proved over more than a century to be convenient reagents for synthesizing derivatives of glutarimide, 3,3-disubstituted glutaric acids [46], azaspiranes [7], etc. A single method has been reported in the literature for the cyclization of Guareschi imides to bispidines (3,7-diazabicyclo[3.3.1]nonane derivatives) under conditions of acid hydrolysis of the nitrile groups [4, 8-11]. The compounds obtained are of interest as intermediate products in the preparation of substances with anti-ischemic activity [12] and of sparteine alkaloids [13]. We have previously reported a convenient method for the synthesis of 4-monosubstituted Guareschi imide salts by the reaction of 3-aryl-2-cyanoacrylamides with cyanoacetylpyrazole [14, 15]. These compounds, and other known 2,6-dioxopiperidine-3,5-dicarbonitriles are of general interest (as C-3/C-5 dinucleophilic reagents) for the preparation of substituted bispidines via a double aminomethylation reaction. The Mannich reaction of 3,5-dinucleophilic pyridine derivatives is one of the most generally applicable methods of preparing 3,7-diazabicyclo[3.3.1]nonanes [16, 17]. However, to this time there was no published evidence for the aminomethylation of Guareschi imides. We have found that the reaction of the glutarimide salt 1a with benzylamine and an excess of formaldehyde occurred under mild conditions to give the 2,4-dioxo-3,7-diazabicyclo[3.3.1]nonane salt (bispidinate) 2. Reaction of salt 1a with -phenethylamine and salt 1b with benzylamine proceeded similarly. Acidification gave the expected bispidines 3a,b. These reactions serve as a first example of the synthesis of 3,7-diazabicyclo[3.3.1]nonane derivatives using Guareschi imides. The structure of compounds 2 and 3a,b was confirmed by IR and H NMR spectroscopy data, HPLC-MS, and elemental analysis. Optimization of the conditions, limits, and potential uses of the reaction will be the subject of future investigations.

The First Example of 3,7-Diazabicyclo[3.3.1]nonane Synthesis by Aminomethylation of Guareschi Imide Salts

2,6-Dioxopiperidine-3,5-dicarbonitriles (also known as Guareschi imides) and their salts are readily prepared by condensation of ketones, cyanoacetic ester, and ammonia [1-3] and have proved over more than a century to be convenient reagents for synthesizing derivatives of glutarimide, 3,3-disubstituted glutaric acids [46], azaspiranes [7], etc. A single method has been reported in the literature for the cyclization of Guareschi imides to bispidines (3,7-diazabicyclo[3.3.1]nonane derivatives) under conditions of acid hydrolysis of the nitrile groups [4, 8-11]. The compounds obtained are of interest as intermediate products in the preparation of substances with anti-ischemic activity [12] and of sparteine alkaloids [13]. We have previously reported a convenient method for the synthesis of 4-monosubstituted Guareschi imide salts by the reaction of 3-aryl-2-cyanoacrylamides with cyanoacetylpyrazole [14, 15]. These compounds, and other known 2,6-dioxopiperidine-3,5-dicarbonitriles are of general interest (as C-3/C-5 dinucleophilic reagents) for the preparation of substituted bispidines via a double aminomethylation reaction. The Mannich reaction of 3,5-dinucleophilic pyridine derivatives is one of the most generally applicable methods of preparing 3,7-diazabicyclo[3.3.1]nonanes [16, 17]. However, to this time there was no published evidence for the aminomethylation of Guareschi imides. We have found that the reaction of the glutarimide salt 1a with benzylamine and an excess of formaldehyde occurred under mild conditions to give the 2,4-dioxo-3,7-diazabicyclo[3.3.1]nonane salt ("bispidinate") 2. Reaction of salt 1a with -phenethylamine and salt 1b with benzylamine proceeded similarly. Acidification gave the expected bispidines 3a,b. These reactions serve as a first example of the synthesis of 3,7-diazabicyclo[3.3.1]nonane derivatives using Guareschi imides. The structure of compounds 2 and 3a,b was confirmed by IR and H NMR spectroscopy data, HPLC-MS, and elemental analysis. Optimization of the conditions, limits, and potential uses of the reaction will be the subject of future investigations.

Synthesis of Fluoroalkylated Heterocycles via the Reaction of 3‐(1‐Hydropolyfluoroalkenyl)‐1‐oxo‐2,4,1‐benzoxazines with Dinucleophilic Reagents.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

Synthesis of Fluoroalkylated Heterocycles via the Reaction of 3‐(1‐Hydropolyfluoroalkenyl)‐1‐oxo‐2,4,1‐benzoxazines with Dinucleophilic Reagents

AbstractThe reaction of 3‐(1‐hydropolyfluoroalkenyl)‐1‐oxo‐2,4,1‐benzoxazines 1 with some dinucleophiles was investigated. 7‐Fluoroalkyl‐2,3‐dihydro‐1,4‐diazepine[1,2‐d]quinazolin‐11‐ones 2, 2‐fluoroalkylisoxazolo[3,2‐b]quin‐azolin‐9‐ones 3 and 2‐fluoroalkylbenzoimidazoles 4 were obtained from the reaction of 1 with 1,2‐diaminoethane, hydroxylamine hydrochloride and 1,2‐diaminobenzene respectively.

The Reaction of 2‐(1‐Hydropolyfluoro‐1‐alkenyl)‐4H‐3,1‐benzoxin‐4‐ones with Dinucleophilic Reagents: A Convenient Route to Fluoroalkylated Nitrogen‐Containing Tricyclic Compounds.

Abstract The reactions of 2-(1-hydropolyfluoro-1-alkenyl)-4H-3,1-benzoxin-4-ones ( 2 ) with hydrazine hydrate and phenyl hydrazine were investigated. The reaction of 2 with hydrazine hydrate in ethanol under reflux condition readily gave 2-fluoroalkyl-4H-pyrazolo[5,1-b]quinazolin-9-ones ( 3 ) in high yields. The reaction of 2 with phenyl hydrazine, however, resulted in the formation of 2-(2-phenyl-5-fluoroalkyl-2H-pyrazol-3-yl) benzoic acids ( 7 ). Further treatment of 7 with PPA gave 1-phenyl-4,9-dihydro-3-fluoroalkyl-1H-pyrozolo[3,4-b]quinolin-4-ones ( 4 ) in 65–80% overall yields.

The reaction of 2-(1-hydropolyfluoro-1-alkenyl)-4 H-3,1-benzoxin-4-ones with dinucleophilic reagents: a convenient route to fluoroalkylated nitrogen-containing tricyclic compounds

The reactions of 2-(1-hydropolyfluoro-1-alkenyl)-4 H-3,1-benzoxin-4-ones ( 2 ) with hydrazine hydrate and phenyl hydrazine were investigated. The reaction of 2 with hydrazine hydrate in ethanol under reflux condition readily gave 2-fluoroalkyl-4 H-pyrazolo[5,1- b]quinazolin-9-ones ( 3 ) in high yields. The reaction of 2 with phenyl hydrazine, however, resulted in the formation of 2-(2-phenyl-5-fluoroalkyl-2 H-pyrazol-3-yl) benzoic acids ( 7 ). Further treatment of 7 with PPA gave 1-phenyl-4,9-dihydro-3-fluoroalkyl-1 H-pyrozolo[3,4- b]quinolin-4-ones ( 4 ) in 65–80% overall yields.

ChemInform Abstract: Diacetylene: A Candidate for Industrially Important Reactions

The review is devoted to industrially important syntheses based on diacetylene, a side product from electrocracking, oxidative pyrolysis of methane and plasmochemical synthesis of acetylene. Reactions of diacetylene and its derivatives with mono- and dinucleophilic reagents occurring in the chemisorption of diacetylene from industrial gases and resulting in stable reactive compounds which can be used as valuable intermediates for organic synthesis and pharmaceutical industry are described. Some specific features of diacetylene reactions in superbasic media are discussed. The bibliography includes 266 references.

Three-membered heterocycles in the synthesis of crown compounds and cryptands (review)

The cyclo-oligomerization of oxirane and aziridine and their derivatives in the presence of BF3 leads to the corresponding macroheterocydic compounds. Crown compounds with exocyclic alkyl, aryl, or functional substituents are formed in the reaction of alkyl-, aryl-, and functionally substituted oxiranes or aziridines with dinucleophilic reagents with subsequent intramolecular cyclocondensation of the reaction products. Methods for the synthesis of cryptands that are based on the reaction of diazacrown compounds with diglycidyl ethers of oligoethyleneglycols are described. The reaction of tosylaziridine with α,Ω-alkylenediamines leads to tetrakis(p-toluenesulfamidoethyl)alkylenediamines, the cyclocondensation of which in the presence of 1,2-dibromomethane under interphase-catalysis conditions gives the corresponding cryptands.

Synthesis of heterocycles from acetylenic carbonyl compounds and dinucleophilic reagents (review)

The literature on reactions of sulfur, oxygen, and nitrogen-containing dinucleophilic reagents with acetylenic carbonyl compounds is reviewed. The mechanisms of some reactions are discussed.

Synthese von 2‐[Benzazolyl‐(2)]‐3,3‐bis‐(alkylthio)‐acrylnitrilen und Umsetzungen mit N‐Nucleophilen

Synthesis of 2‐[Benzazolyl‐(2)]‐3,3‐bis‐(alkylthio)‐acrylnitriles and Their Reactions with N‐NucleophilesThe reactions of benzazolyl‐(2)‐acetonitriles 1 (1H‐benzimidazolyl‐, 1‐methylbenzimidazolyl‐, benzoxazolyl‐ and benzothiazolyl‐) with carbon disulfide in the presence of sodium hydride in dimethylsulfoxide and methylation yield the 2‐[benzazolyl‐(2)]‐3,3‐bis‐(alkylthio)‐acrylonitriles 3–5 reacting with amines to the keten‐S,N‐acetals 6–9.If dinucleophilic reagents are used heterocyclic systems 10–14 are formed.

Heterocycles from N‐benzoylthioamides and dinucleophilic reagents

AbstractN‐Benzoylthioamides (1) react with hydrazines and hydroxylamine to form 1H‐1,2,4‐triazoles and 1,2,4‐oxadiazoles, respectively. A similar treatment of the S‐methyl derivatives of 1 with amidines leads to 1,3,5‐triazines. Ethyl ZV‐benzoylthiocarbamate undergoes analogous reactions to yield the corresponding ethoxyheterocycles.

ChemInform Abstract: HETEROCYCLES FROM N‐ETHOXYCARBONYLTHIOAMIDES AND DINUCLEOPHILIC REAGENTS. 2. FIVE‐MEMBERED RINGS CONTAINING TWO HETEROATOMS AT 1,3 POSITIONS

Chemischer InformationsdienstVolume 8, Issue 27 Heterocyclic Compounds ChemInform Abstract: HETEROCYCLES FROM N-ETHOXYCARBONYLTHIOAMIDES AND DINUCLEOPHILIC REAGENTS. 2. FIVE-MEMBERED RINGS CONTAINING TWO HETEROATOMS AT 1,3 POSITIONS B. GEORGE, B. GEORGESearch for more papers by this authorE. P. PAPADOPOULOS, E. P. PAPADOPOULOSSearch for more papers by this author B. GEORGE, B. GEORGESearch for more papers by this authorE. P. PAPADOPOULOS, E. P. PAPADOPOULOSSearch for more papers by this author First published: July 5, 1977 https://doi.org/10.1002/chin.197727206Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume8, Issue27July 5, 1977 RelatedInformation

Heterocycles from N-ethoxycarbonylthioamides and dinucleophilic reagents. 3. Six- and seven-membered rings with two or three heteroatoms

Heterocycles from N-ethoxycarbonylthioamides and dinucleophilic reagents. 3. Six- and seven-membered rings with two or three heteroatoms

Heterocycles from N-ethoxycarbonylthioamides and dinucleophilic reagents. 2. Five-membered rings containing two heteroatoms at 1,3 positions

Heterocycles from N-ethoxycarbonylthioamides and dinucleophilic reagents. 2. Five-membered rings containing two heteroatoms at 1,3 positions