Solvent‐Free Synthesis of Heterocyclic Thioureas Using Microwave Technology

A new and rapid solvent‐free synthesis of heterocyclic thioureas in a microwave oven has been reported for the first time. Nine heterocyclic thioureas that possess biological activity have been synthesized. The reaction time is short (2–4.5 min) and gives excellent yields (82.9–95.5%).     

A Convenient Synthesis of Hindered N-Aryl Substituted Cyclic Amines

An efficient and high yielding synthesis of N-substituted pyrrolidines and piperidines is described.     

A Convenient Approach for Synthesis of (Z)-3-Butylidenephthalide Derivatives

The reaction of n-Bul, i with phthalic anhydride derivatives leads to (Z)-3-butylidenephthalide derivatives.     

Synthesis of Guanylhydrazones Under Microwave Irradiation

Abstract

The reaction of aromatic aldehydes and ketones with aminoguanidine hydrochloride under microwave irradiation (MWI) afforded guanylhydrazones in shorter reaction times and improved yield as compared to the conventional methodology.     

Synthesis of Azafluorenones using Zeolites.

A convenient method for the synthesis of various azafluorenones (2a-f & 4a-d) by cyclization of substituted arylpyridines (1a-f & 3a-d) using zeolites are described.     

Synthesis of 5-Cyanoindazole and 1-Methyl and 1-Aryl-5-Cyanoindazoles

5-Cyanoindazoles are conveniently prepared in two to three steps from commercially available 5-bromo-2-fluorobenzaldehyde.     

Regioselective Synthesis of Novel Spirooxindolo and Spiroindano Nitro Pyrrolidines Through 3+2 Cycloaddition Reaction

β‐Nitro styrene reacts with nonstabilized azomethine ylides generated from isatin/ninhydrin with sarcosine, resulting in the formation of a series of spiroxindolo nitro pyrrolidines, and spiroindano nitro pyrrolidines, respectively, in good yields. It was noted that in a one‐pot 3+2 cycloaddition reaction, the azomethine ylides generated from isatin and ninhydrin have reacted with the β‐nitro styrenes regiochemically in opposite ways.     

Synthesis of 1H‐Imidazoles Catalyzed by Cu‐Nanoparticle and Its Physicochemical Properties

Series of 1‐arylmethyl‐4, 5‐dihydro‐2‐aryl‐1H‐imidazole were synthesized expeditiously in good yields from 1,2‐diaminoethane and aromatic aldehydes in the presence of Cu nanoparticle under microwave irradiation in solvent‐free method. Monodisperse spherical Cu nanoparticles with a diameter range of 45 ± 8 nm were synthesized by polyol process. The particle size and elemental structure of copper nanoparticles were confirmed by XRD data and was found to be having a face‐centered cubic structure. The resulting substituted imidazoles have been studied in the achievement of degree of drug absorption enhancement as well as the potential associated toxicity on the basis of hypothetical antibacterial pharmacophores and structures that were designed to interact with both of gram‐positive and gram‐negative bacteria. All the synthesized molecules were characterized on the basis of 1H NMR, 13C NMR, mass spectrometry, and elemental data.     

InCl3‐Driven Regioselective Synthesis of Functionalized/Annulated Quinolines: Scope and Limitations

The efficient, regioselective synthesis of functionalized/annulated quinolines was achieved by the coupling of 2‐aminoaryl ketones with alkynes/active methylenes/α‐oxoketene dithioacetals promoted by InCl₃ in refluxing acetonitrile as well as under solvent‐free conditions in excellent yields. This transformation presumably proceeded through the hydroamination–hydroarylation of alkynes, and the Friedländer annulation of active methylene compounds and α‐oxoketene dithioacetals with 2‐aminoarylketones. In addition, simple reductive and oxidative cyclization of 2‐nitrobenzaldehyde and 2‐aminobenzylalcohol, respectively, afforded substituted quinolines. Systematic optimization of the reaction parameters allowed us to identify two‐component coupling (2CC) conditions that were tolerant of a wide range of functional groups, thereby providing densely functionalized/annulated quinolines. This approach tolerates the synthesis of various bioactive quinoline frameworks from the same 2‐aminoarylketones under mild conditions, thus making this strategy highly useful in diversity‐oriented synthesis (DOS). The scope and limitations of the alkyne‐, activated methylene‐, and α‐oxoketene dithioacetal components on the reaction were also investigated.     

Conformationally Restricted Analogues of Tryptophan: Synthesis of Chiral 3-Amino-4-indolyl-2-piperidones

Abstract

The {Trp-phenylglycinol} pseudodipeptide (αR,3R?,4R?)-N-(2-acetoxy-1-phenylethyl)-3-amino-4-indolyl-2-piperidone 33 has been synthezised by condensation of the 3-amino-substituted anhydride 30 with (R)-(-)-phenylglycinol followed by reduction of the resulting imide.     

Enantioselective Synthesis of Boron‐Substituted Quaternary Carbon Stereogenic Centers through NHC‐Catalyzed Conjugate Additions of (Pinacolato)boron Units to Enones

The first examples of Lewis base catalyzed enantioselective boryl conjugate additions (BCAs) that generate products containing boron‐substituted quaternary carbon stereogenic centers are disclosed. Reactions are performed in the presence of 1.0–5.0 mol % of a readily accessible chiral accessible N‐heterocyclic carbene (NHC) and commercially available bis(pinacolato)diboron; cyclic or linear α,β‐unsaturated ketones can be used and rigorous exclusion of air or moisture is not necessary. The desired products are obtained in 63–95 % yield and 91:9 to >99:1 enantiomeric ratio (e.r.). The special utility of the NHC‐catalyzed approach is demonstrated in the context of an enantioselective synthesis of natural product antifungal (?)‐crassinervic acid.     

A Convenient Synthesis of 2-Oxazolines and 2-Benoxazoles with PPh3-DDQ as the Dehydrating Reagent

2‐Oxazolines and 2‐benoxazoles were synthesized in high yields from acylamino alcohols and acylamino‐ phenols, respectively, with triphenylphosphine‐2,3‐dichloro‐5,6‐dicyanobenzoquinone (PPh₃‐DDQ) as the dehydrating and activating reagent. The synthesis was accomplished under neutral conditions.     

4,5,6-三取代-2H-吡喃-2-酮的简便合成法

2H-吡喃-2-酮及其衍生物是有机合成的蓬要中间体。对于它们的合成已有许多报道,例如利用烯醇醚或烯醇砖醚与丁酰氯反应;羰基化合物与甲氧亚甲螭丙二酸二甲酯反应;α-苯基丙醛酸酯与丙酮的成环缩合2,6-二氯-3-三氯甲基吡啶与亚甲基丁二酸酯的反应,邻氰基苯乙炔、二苯乙二酮和丙酮的反应。但上述方法往往原料较难得到,产率较低或操作麻烦。     

A Facile One‐Step Synthesis of 2‐Arylindazoles via Reductive Cyclization of N‐(2‐nitroarylidene)amines

A mild and efficient synthesis of 2‐arylindazole derivatives via the reductive cyclization of nitro‐aryl substrates mediated by a low‐valent titanium reagent (TiCl₄/Sm/Et₃N) has been developed. The attractive features of the current method include an N–N bond formation and the selective reduction of the C = N bond and nitro group, both of which were easily achieved in one‐pot by controlling the pH of the reaction mixture.     

A New Route to N‐Aryl 2‐Alkenamides,N‐Allyl N‐Aryl 2‐Alkenamides,and N‐Aryl α,β‐Unsaturated γ‐Lactams from N‐Aryl 3‐(Phenylsulfonyl)propanamides

A series of N‐aryl 2‐alkenamides were produced efficiently by treating N‐aryl 3‐(phenylsulfonyl)‐propanamides with potassium tert‐butoxide in THF at 0°C. With out isolation, it was further treated with an additional equivalent of potassium tert‐butoxide and allyl bromide to give N‐allyl N‐aryl 2‐alkenamides in one pot in good yields. Followed by a ring‐closing metathesis reaction, these N‐allyl N‐aryl 2‐alkenamides were respectively converted into corresponding N‐aryl α,β‐unsaturated γ‐lactams in moderate yields.     

Regioselective annelation of 3-(prop-2-ynylsulfanyl)-1,2,4-benzotriazine to thiazolo[2,3-c][1,2,4]benzotriazine

Summary Thiosemicarbazide reacted with 1,2-diaminobenzene to give 1,2-dihydro-3-thioxo-1,2,4-benzotriazine (1) in fairly good yield in a solvent free reaction under microwave irradiation.1 was condensed with prop-2ynyl bromide in the presence of sodium methoxide to afford the corresponding 3-(prop-2-ynylsulfanyl)-1,2,4-benzotriazine (5). Transformation of5 to 3-methylidene-2,3-dihydro-9H-thiazolo[2,3-c][1,2,4]benzotriazine (6) was performed in the presence of a palladium salt.

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Regioselektive Anellierung von 3-(prop-2-inylsulfanyl)-1,2,4-benzotriazin zu Thiazolo[2,3-c][1,2,4]benzotriazin

Zusammenfassung Thiosemicarbazid reagierte mit 1,2-Diaminobenzol ohne Lösungsmittel und unter Bestrahlung mit Mikrowellen in guter Ausbeute zu 1,2-Dihydro-3-thioxo-1,2,4-benzotriazin (1), welches in Gegenwart von Natriummethoxid mit Prop-2-inylbromid zum entsprechenden 3-(Prop-2-inylsulfanyl)-1,2,4-benzotriazin (5) kondensiert wurde. Die Umsetzung von5 zu Methyliden-2,3-dihydro-9H-thiazolo[2,3-c] [1,2,4]benzotriazin (6) gelang unter Palladiumkatalyse.

     

Microwave‐Assisted Convenient Synthesis of α,β‐Unsaturated Esters and Ketones via Aldol‐Adduct Elimination

Various fluorinated 3‐oxo ester/1,3‐diketones were reacted with carbonyl compounds, in presence of piperidine and under microwave irradiation, to afford (E)‐α,β‐unsaturated esters and ketones in good yields. The systematic study reveals that the reaction proceeded through the formation of aldol adduct. The method provides a new and simple way for C,C bond formations.     

Hypervalent Iodine in Synthesis XXXV: A Simple and Convenient Stereospecific Synthesis of Vinyl Esters of Dithiocarbamic Acids

Vinyl esters of dithiocarbamic acids have been stereospecifically prepared by the reaction of sodium dithiocarbamates with vinyi(phenyi)iodonium tetrafluoroborates with retention or inversion of the configurations.