Title: Synthesis of nitrogen-containing medium-sized rings fused with benzene or indole through transition metal-catalyzed carbocyclizations
Other Titles: Synthese van stikstof-bevattende ringen van medium-grootte, gefuseerd met benzeen of indool, via transitiemetaal-gekatalyseerde carbocyclisaties
Authors: Peshkov, Vsevolod; S0209865
Issue Date: 2-Jul-2013
Abstract: 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;}Thisthesis is devoted to the exploration of the strategies for the synthesis ofnitrogen-containing medium-sized rings fused with benzene or indole. Theimplemented approaches are based on several carbocyclization reactionsdeveloped previously in our laboratory which involve the construction of thekey C-C bond with the simultaneous assembly of the medium-sized ring. The elaboratedprotocols rely on modern transition metal catalysis and utilize readilyavailable starting materials.Chapter 1 serves as anintroduction into the chemistry of the title heterocycles, highlighting theiroccurrence in nature, biological properties and existing methodologies fortheir synthesis. The goals of the current research are also summarized in thischapter.Chapter 2 is dedicatedto the diversification of the 3-benzazepine scaffold using A3-couplingas a tool for the generation of propargylamine precursors for furtherPd-catalyzed intramolecular alkyne hydroarylation (reductive Heck reaction).Chapter 3 describesthe development of a novel protocol for a tandem Heck-Suzuki reaction and itsfurther application for diversification of the 3-benzazepine scaffold. A broadoptimization survey as well as detailed studies on the scope and limitations ofthis procedure are included.Chapter 4 deals withthe application of the Pd-catalyzed intramolecular alkyne hydroarylationreaction for the construction of the azocino[4,5,6-cd]indole framework. Some interesting structural features of thetitle heterocycles are commented.Chapter 5 discussesthe elaboration of the AuPPh3Cl/AgOTf-catalyzed protocol for the intramolecular alkyne hydroarylation processleading to azocino[5,4-b]indoles. A close look on thereactions with terminal propargylic amides resulted in the isolation and characterizationof hitherto unknown cyclized products interesting for the mechanisticunderstanding of such processes.Finally, General conclusions and perspectives arehighlighted.
Publication status: published
KU Leuven publication type: TH
Appears in Collections:Molecular Design and Synthesis

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