000203264 001__ 203264
000203264 005__ 20190317000041.0
000203264 0247_ $$2doi$$a10.5075/epfl-thesis-6453
000203264 02470 $$2urn$$aurn:nbn:ch:bel-epfl-thesis6453-9
000203264 02471 $$2nebis$$a10271696
000203264 037__ $$aTHESIS
000203264 041__ $$aeng
000203264 088__ $$a6453
000203264 245__ $$a"New methods for indoles and [3,4]-fused oxindoles syntheses" and "Copper-catalyzed/mediated difunctionalization of alkenes with alkylnitriles"
000203264 269__ $$a2014
000203264 260__ $$aLausanne$$bEPFL$$c2014
000203264 336__ $$aTheses
000203264 502__ $$aProf. N. Cramer (président) ; Prof. J. Zhu (directeur) ; Prof. O. Baudoin,  Prof. E. Gwilherm,  Prof. X. Hu (rapporteurs)
000203264 520__ $$aTwo main topics were addressed in this manuscript: (1) New methods for indoles and [3,4]-fused oxindoles syntheses; (2) Copper-catalyzed/mediated difunctionalization of alkenes with alkylnitriles. Given the omnipresent character of the indole and oxindole ring systems, their synthesis and functionalization are a research area of main interest. Two different strategies have been developed for the indole motif synthesis. The first method implies a Cucatalyzed heteroannulation of ortho-aminophenylboronic ester and β-ketoester under mild, base free conditions. The second strategy consists in the synthesis of N-arylindoles via a benzannulation reaction with α-N-aryl aminoketone and 2-(trimethylsilyl)phenyl trifluoromethanesulfonate as benzyne precursor. The benzannulation reaction was applied to the synthesis of 5,6-dihydroindolo[1,2-a]quinolone by using cyclic α-N-aryl aminoketone, obtained in one step from commercial compounds via the three-component Povarov reaction. Afterwards, we developed a novel Pd(0)-catalyzed domino reaction, involving carbopalladation/1,4-Pd shift via double C-H bond activation/C-C bond formation for the synthesis of [3,4]-fused oxindoles. In the second part of the manuscript, we addressed the copper-catalyzed difunctionalization of alkenes. The difunctionalization of olefin represents a domain of main interest in organic synthesis due to the availability of the starting material and the possibility to reach high complexity and diversity of products in one single step. We developed a methodology that allows the introduction of a "C(R')(R)CN" group by coppercatalyzed difunctionalization of alkene, using the alkyl nitriles as reaction partner. By applying this methodology, different functionalized classes of compounds were synthesized: phthalides, γ-lactone and isochromanones, epoxides and ketones.
000203264 6531_ $$aIndole
000203264 6531_ $$aN-arylindole
000203264 6531_ $$aaryne
000203264 6531_ $$apalladium
000203264 6531_ $$adomino-reaction
000203264 6531_ $$a[3
000203264 6531_ $$a4]-fused oxindole
000203264 6531_ $$aalkene difunctionalization
000203264 6531_ $$acopper
000203264 6531_ $$anitrile
000203264 700__ $$0244944$$aBunescu, Ala$$g205967
000203264 720_2 $$0244710$$aZhu, Jieping$$edir.$$g206332
000203264 8564_ $$s6547648$$uhttps://infoscience.epfl.ch/record/203264/files/EPFL_TH6453.pdf$$yn/a$$zn/a
000203264 909C0 $$0252341$$pLSPN$$xU12326
000203264 909CO $$ooai:infoscience.tind.io:203264$$pthesis-bn2018$$pDOI$$pSB$$pthesis$$qDOI2$$qGLOBAL_SET
000203264 917Z8 $$x108898
000203264 917Z8 $$x108898
000203264 917Z8 $$x108898
000203264 918__ $$aSB$$cISIC$$dEDCH
000203264 919__ $$aLSPN
000203264 920__ $$a2014-11-14$$b2014
000203264 970__ $$a6453/THESES
000203264 973__ $$aEPFL$$sPUBLISHED
000203264 980__ $$aTHESIS