Рябухін С. Systems based on trimethylsilyl halides for heterocyclization

The thesis is devoted to the establishment of condensing systems based on trimethylsilyl halides. The efficiency of TМSCl as a promoter for the creation of combinatorial libraries of substituted N heterocycles was demonstrated by classical heterocyclizations that take place with the formation of the C¬–N bond. By the quantum mechanical calculations, it has been shown that the universality of TМSHal as condensing agents can be related to forming of rather strong chemical adducts with diferent ligands corresponding to local minima of energy. By recyclization of formylchromones under action of 1,3-CCN-binucleophiles (2-R-acetamides, 2 (R methyl)benzodiazoles and imidazoles and 2-(R-methyl)-pyrimidine-4-one) in the medium of TМSCl / DMF it was synthesized a large number of pyridopyrimidines with 2 hydroxybenzoyl residue. An effective methodology for the preparation of 3-(2-hydroxybenzoyl)quinolines and 7H chromeno[3,2-c]quinoline-7-ones of 3 formylchromones and a wide variety of anilines using TМSCl as a promoter in the synthesis of Comba was developed. An efficient approach to the synthesis of previously inaccessible 5 heteraryl-3 (2 hydroxybenzoyl)pyrroles and derivatives of 4-(2-hydroxybenzoyl)-1H pyrrole-2 carboxylic acid from 3-formylchromones and hetarylmethylamines or derivatives of glycine in the medium of TМSCl was studied. The advantages of using TМSCl in the Friedländer reaction in comparison with classical methods are shown, namely: chemo-selectivity; the possibility of using methylene components with low C–H acidity or with hindered reaction center; the absence of hydrolysis of ester or amide substituents in the target quinoline; the possibility of 3-fluoro(chloro,bromo)quinolines’ obtaining; the suitability for the synthesis of a wide collection of heteroanalogues of quinolines and 3 halogenoquinolineі on the basis of α-amino-β keto¬heterocyclic derivatives.