I. V. Aksenova

Metal-free transannulation reaction of indoles with nitrostyrenes: a simple practical synthesis of 3-substituted 2-quinolones.

3-Substituted 2-quinolones are obtained via a novel, metal-free transannulation reaction of 2-substituted indoles with 2-nitroalkenes in polyphosphoric acid. The reaction can be used in conjunction with the Fisher indole synthesis offering a practical three-component heteroannulation methodology to produce 2-quinolones from arylhydrazines, 2-nitroalkenes and acetophenone.

Metal-free ring expansion of indoles with nitroalkenes: a simple, modular approach to 3-substituted 2-quinolones

3-Substituted 2-quinolones are obtained via a novel metal-free transannulation reaction of 2-nitroolefins with 2-substituted indoles in polyphosphoric acid. This acid-mediated cascade transformation operates via the ANRORC (Addition of Nucleophile, Ring Opening, and Ring Closure) mechanism and can be used in combination with the Fisher indole synthesis to offer a practical three-component hetero-annulation approach to 2-quinolones from arylhydrazines, 2-nitroalkenes, and acetophenone. An alternative entry to this chemistry employing the alkylation of electron-rich arenes and hetarenes with 1-(2-indolyl)-2-nitroalkene has also been demonstrated.

Activity of 2-aryl-2-(3-indolyl)acetohydroxamates against drug-resistant cancer cells.

Many types of tumor, including glioma, melanoma, non-small cell lung, esophageal, and head and neck cancer, among others, are intrinsically resistant to apoptosis induction and poorly responsive to current therapies with proapoptotic agents. In addition, tumors often develop multidrug resistance based on the cellular efflux of chemotherapeutic agents. Thus, novel anticancer agents capable of overcoming these intrinsic or developed tumor resistance mechanisms are urgently needed. We describe a series of 2-aryl-2-(3-indolyl)acetohydroxamic acids that are active against apoptosis- and multidrug-resistant cancer cells as well as glioblastoma neurosphere stemlike cell cultures derived from patients. Thus, the described compounds serve as a novel chemical scaffold for the development of potentially highly effective clinical cancer drugs.

Nitromethane in Polyphosphoric Acid—A New Reagent for Carboxyamidation and Carboxylation of Activated Aromatic Compounds

Abstract A new method of carboxyamidation of aromatic compounds based on their reaction with nitromethane in polyphosphoric acid has been developed. Upon the hydrolysis of benzamides during the reaction mixture workup, the corresponding benzoic acids can be obtained. GRAPHICAL ABSTRACT

Organic chemistry. History and mutual relations of universities of Russia

The review describes the history of development of organic chemistry in higher schools of Russia over a period of 170 years, since the emergence of organic chemistry in our country till now.

Formylation of perimidine derivatives in a system 1,3,5-triazine-polyphosphoric acid

The application of compound II in the role of formylating agent is well known [2]. In the classical version the reaction is carried out without catalyst or in the presence of Lewis acids. We demonstrated that under these conditions the perimidine formylation did not occur. Therefore another combination of reagents was used as formylating agent: 3-fold excess of 1,3,5-triazine II in 80% polyphosphoric acid (PPA) at 55–60°C. The yield of aldehydes IV under these conditions was 83–91%.

peri Annelation of Perimidines in Reactions with 1,3-Dicarbonyl Compounds*

A new approach to 1,3-diazapyrenes via peri annelation of perimidines with 1,3-dicarbonyl compounds is developed. It is demonstrated that this method has a number of advantages compared to a previously reported procedure employing chalcones as electrophilic components. The new method can be used for efficient double peri annelation of biperimidines with 1,3-dicarbonyl compounds affording 2,2′-bi-1,3-diazapyrenes.

Synthesis of 1,3-diazapyrenes by vinylformylation of perimidines

Several methods for the synthesis of 1,3-diazapyrene derivatives have been reported previously [1 5]. However, these methods suffer from poor yields and lack of general character. In the present communication we describe a procedure that is free from the above disadvantages. The procedure is based on the vinylformylation of heterocyclic compounds, which has been developed relatively recently [6]. We have found that perimidines Ia Ic react with 3-(Nmethyl-N-phenylamino)acrolein in dichloroethane in the presence of POCl3 to give the corresponding 1,3diazapyrenes IIIa IIIc in 42 56% yields.

Oxidative coupling of tetraalkynyltin with aldehydes leading to alkynyl ketones

The reaction of tetraalkynyltin with aldehydes was studied for the first time. The reaction was shown to proceed as a tandem process of nucleophilic addition of tin acetylide to aldehyde followed by Oppenauer-type oxidation of produced tin alcoholates, and may be used as a convenient one-pot approach to acetylenic ketones. The advantages and limitations of the proposed method are discussed.

Some problems of the teaching of organic chemistry in universities of Russia

Original Russian Text