Silver(I) triflate-catalyzed protocol for the post-ugi synthesis of spiroindolines

A silver(I) triflate-catalyzed protocol for the post-Ugi synthesis of tetracyclic spiroindolines has been developed. The protocol worked best for indole-3-carbaldehyde-derived Ugi adducts obtained using anilines and 3-aryl propiolic acids. Thus, it is complementary to the previous cationic gold-catalyzed procedure that was developed for analogues Ugi substrates derived from aliphatic amines and 3-alkyl propiolic acids. Furthermore, we have demonstrated that under our new settings this domino Friedel-Crafts ipso cyclization / imine trapping process could be efficiently combined with the preceding four-component Ugi reaction into a two-step one-pot transformation

Щодо кола принципів призначення покарання

Перешивко О. С. Щодо кола принципів призначення покарання / О. С. Перешивко // Актуальні проблеми держави і права: зб. наук. пр. / редкол.: С. В. Ківалов (голов. ред.), В. М. Дрьомін (заст. голов. ред.), Ю. П. Аленін [та ін.]; МОН України, НУ ОЮА. – Одеса: Юрид. л-ра, 2013. – Вип. 70. - С. 284-289.У статті висвітлено основні підходи до визначення кола принципів призначення покарання. Визначено роль кожного з них в обранні конкретного виду та міри покарання особі, винній у вчиненні злочину. Обґрунтовується необхідність законодавчого визначення кола принципів призначення покарання

The Groebke-Blackburn-Bienayme Reaction

Imidazo[1,2a]pyridine is a well‐known scaffold in many marketed drugs, such as Zolpidem, Minodronic acid, Miroprofen and DS‐1 and it also serves as a broadly applied pharmacophore in drug discovery. The scaffold revoked a wave of interest when Groebke, Blackburn and Bienaymé reported independently a new three component reaction resulting in compounds with the imidazo[1,2‐a]‐heterocycles as a core structure. During the course of two decades the Groebke Blackburn Bienaymé (GBB‐3CR) reaction has emerged as a very important multicomponent reaction (MCR), resulting in over a hundred patents and a great number of publications in various fields of interest. Now two compounds derived from GBB‐3CR chemistry received FDA approval. To celebrate the first 20 years of GBB‐chemistry , we present an overview of the chemistry of the GBB‐3CR, including an analysis of each of the three starting material classes, solvents and catalysts. Additionally, a list of patents and their applications and a more in‐depth summary of the biological targets that were addressed, including structural biology analysis, is given

Transition metal-catalyzed cycloisomerizations of propargylic ureas and guanidines derived in situ from secondary propargylamines

Normal 0 false false false MicrosoftInternetExplorer4 /* Style Definitions */ table.MsoNormalTable {mso-style-name:"Обычная таблица"; mso-tstyle-rowband-size:0; mso-tstyle-colband-size:0; mso-style-noshow:yes; mso-style-parent:""; mso-padding-alt:0pt 5.4pt 0pt 5.4pt; mso-para-margin:0pt; mso-para-margin-bottom:.0001pt; mso-pagination:widow-orphan; font-size:10.0pt; font-family:"Times New Roman"; mso-ansi-language:#0400; mso-fareast-language:#0400; mso-bidi-language:#0400;}This thesis is devoted to the exploration of synthetic strategies for the generation of secondary N-alkylpropargylamines, aswell as to the study of their synthetic utility for the construction of smallheterocycles. A substantial part of this work deals with additions of secondary propargylamines tovarious heteroallennes, followed by transition metal-catalyzedcycloisomerizations. Also special attention is given to the regio- andchemoselectivity of these processes in the context of existing methodologies.The elaborated protocols rely on modern transition metal catalysis and utilizereadily available starting materials.Chapter1 serves as anintroduction to the chemistry of propargylamines in general, and secondary N-alkylpropargylamines inparticular, highlighting the A3-coupling reaction as a modernmethod for their synthesis. Several processes which are relevant to the presentstudy and which utilize secondary N-alkylpropargylaminesas starting materials, are also briefly outlined. The objectives of thecurrent research are summarized in this chapter.Chapter2 is dedicated to theelaboration of microwave-assisted Cu(I)-catalyzed coupling of a ketone, analkyne and a primary amine (KA2-coupling), providing a generalaccess to quaternary carbon-containing secondary N-alkylpropargylamines.Chapter3 describes theapplication of the above propargylamines in the Ag(I)-mediated tandem guanylation/cycloisomerizationreaction previously developed in our group, in order to access a structurallyinteresting class of heterocycles featuring a spiro-cyclic guanidine unit.Chapter4 deals with acomparative study on transition metal-catalyzed cycloisomerizations of propargylicureas derived in situ from secondarypropargylamines and tosyl isocyanate. The influence of the catalytic system onthe reaction outcome was thoroughly studied with two model examples, resultingin the establishment of two selective protocols for both O- and N-cyclizations,leading to oxazolidin-2-imines and imidazolidin-2-ones, respectively. Anattempt to rationalize the observed chemoselectivity is given.Chapter5 is dedicated to theunexpected regio- and chemoselectivity of cationic gold-catalyzedcycloisomerizations of propargylic ureas derived in situ from secondary propargylamines and aryl or alkylisocyanates, providing an efficient access to the 3,4-dihydropyrimidin-2(1H)-one core.Finally,General conclusions and perspectives are highlighted.status: publishe