6 research outputs found
Development of methodologies toward amineâs α,ÎČ-functionalization : Synthesis and application of rigid spirobiindane organocatalysts
Cette thĂšse se divise en trois parties. La premiĂšre partie concerne nos approches vers la fonctionnalisation rĂ©giosĂ©lective dâimines, gĂ©nĂ©rĂ©es in situ dans le milieu rĂ©actionnel. En particulier, nous avons dĂ©veloppĂ© une mĂ©thode de synthĂšse dâα-amidosulfures qui furent ensuite utilisĂ©s comme plateforme pour accĂ©der Ă des α-aryles amines aliphatiques par rĂ©action de Friedel-Crafts dĂ©clenchĂ©e par du NIS. La seconde partie de ce travail rapporte la synthĂšse de spirobiindane rigides optiquement actifs, que nous avons ensuite utilisĂ©s comme plateforme pour former des organocatalyseurs de type acides phosphoriques. Ces derniers furent ensuite exploitĂ©s dans le dĂ©veloppement dâune rĂ©action de cycloaddition [3+2] -optionnellement amorcĂ©e par du PIDA- donnant accĂšs Ă des 2,3-dihydrobenzofuranes optiquement actifs. Enfin, dans une derniĂšre partie, deux sĂ©quences rĂ©actionnelles furent dĂ©veloppĂ©es, donnant accĂšs Ă des iodoarĂšnes iodĂ©s : les BINIs et SPINIs ortho-diarylĂ©s. Ces structures furent engagĂ©es en organocatalyse, et ont permis dâapporter une approche rationnelle aux mĂ©canismes dâinduction asymĂ©trique impliquant des espĂšces iodĂ©s hypervalentes.This thesis is divided in three parts. The first part deals with our approaches toward regioselective functionalization of in situ generated imines. In particular, we had developed a synthesis of α-amidosulfides, which were used as substrates to access aliphatics α-aryles amines through a NIS-triggered Friedel-Crafts reaction. Second part of this work describe the synthesis of spirobiindane-based organocatalysts, which were used in a [3+2] cycloaddition - optionally triggered with PIDA - leading to optically actives 2,3-dihydrobenzofurans. Finally, two synthetic pathways were developed to form new class of aryliodides: diaryls BINIs & SPINIs. Those scaffolds were exploited to bring a rational explanation of chirality transfer in reactions using hypervalent iodine species
Cerium(IV) Ammonium Nitrate Mediated Three-Component 뱉Allylation of Imine Surrogates
A general
and practical CAN-mediated oxidative radical α-coupling
reaction of various imine surrogates with allylsilanes has been described.
This multicomponent process affords ÎČ-allylated α-carbamido
ethers as stable imine precursors in respectable yields under mild
conditions
Chiral Phosphoric Acid Catalyzed Inverse-Electron-Demand Aza-DielsâAlder Reaction of Isoeugenol Derivatives
Highly enantio- and diastereoselective three-component inverse electron-demand aza-DielsâAlder reaction of aldehydes, anilines, and isoeugenol derivatives catalyzed by a chiral phosphoric acid catalyst are reported. A wide variety of 2,3,4-trisubstituted tetrahydroquinolines containing an aryl group at the 4-position were obtained in a one-pot process with good to high yields and excellent stereoselectivities (>95:5 dr and up to >99% ee)
Chiral Phosphoric Acid Catalyzed Inverse-Electron-Demand Aza-DielsâAlder Reaction of Isoeugenol Derivatives
Highly enantio- and diastereoselective three-component inverse electron-demand aza-DielsâAlder reaction of aldehydes, anilines, and isoeugenol derivatives catalyzed by a chiral phosphoric acid catalyst are reported. A wide variety of 2,3,4-trisubstituted tetrahydroquinolines containing an aryl group at the 4-position were obtained in a one-pot process with good to high yields and excellent stereoselectivities (>95:5 dr and up to >99% ee)
Chiral Phosphoric Acid Catalyzed [3 + 2] Cycloaddition and Tandem Oxidative [3 + 2] Cycloaddition: Asymmetric Synthesis of Substituted 3âAminodihydrobenzofurans
Asymmetric
[3 + 2] cycloaddition of quinones with ene- and thioene-carbamates
was achieved by chiral phosphoric acid catalysis, providing the corresponding
3-amino-2,3-dihydrobenzofurans in excellent yields with moderate to
good diastereoselectivities and excellent enantioselectivities. An
asymmetric tandem oxidative cycloaddition protocol starting from hydroquinones
was also accomplished with phenyliodineÂ(III) diacetate and a chiral
phosphoric acid in the same reaction vessel