60 research outputs found
Vinylogous aldol reaction of heterocyclic silyloxy dienes. Application in synthesis
A versatile, readily accessible triad of 2-enoxy silane synthons derived from furan,
pyrrole, and thiophene is presented. These heterocycles, in reacting with carbonyl and carbonyl-
related acceptors, act as vinylogous nucleophile modules, giving rise to diverse, functionality-
rich, Îł-substituted α,ÎČ-unsaturated carbonyl constructs. These, in turn, are invaluable
platforms onto which further functional elements and chirality may be introduced. A
couple of appealing applicationsâthe variable construction of a repertoire of carbasugars
and a library of annonaceous acetogenin segmentsâhave been chosen to illustrate the viability
of this vinylogous aldol approach
Exploring the boundaries of vinylogous Mukaiyama aldol processes: stereoselective access to polyunsaturated homoallylic alcohols
Catalytic enantioselective vinylogous aldol reactions using extended enolates are of prominent value in synthetic organic chemistry. Here, we report our advances in the
development of enantioselective bis-vinylogous and hyper-vinylogous Mukaiyama aldol reactions between a series of polyenylsilyloxy furans or polyenylsilyoxy indoles and
aromatic aldehydes, realized by use of the enabling catalyst combination of silicon tetrachloride and Denmarkâs chiral bis-phosphoramide base (R,R)-I. Several crucial
issues such as the remote site-, enantio- and geometrical selectivity of the reaction will be highlighted, ultimately focusing on one main question: how far can we push the
limits of the vinylogous reactivity transmittal?</i
Nuove metodologie d'accesso alla diversitĂ molecolare: sintesi di biomolecole e loro insiemi per un utilizzo in agricoltura e terapia
La nostra metodologia totalmente sintetica ed altamente flessibile indirizzata alla costruzione di
piccole molecole organiche chirali, sia individuali, sia in miscela fra loro, prevede lâutilizzo di una
triade omogenea di reagenti nucleofili eterociclici contenenti, rispettivamente, ossigeno, azoto e
zolfo
Sintesi totale di amminoacidi a base ciclitolica: un approccio orientato alla diversitĂ
Amminoacidi carbociclici con funzionalitĂ multiple installate sulle varie posizioni anulari,
come le strutture polioliche 1-8 di questo studio, rappresentano un insieme molecolare
omogeneo e, allo stesso tempo, variato, in cui ciascuna entitĂ puĂČ essere vista sotto diverse
angolazioni
Nuovi motivi azabiciclo [X.2.1] alcanici
Abbiamo intrapreso uno studio accurato avente
come oggetto la reazione tra un reagente silossidienico a base pirrolica il N-(terzbutilossicarbonil)-
2-(terz-butildimetilsililossi)pirrolo (TBSOP, 1), e una serie di accettori chetonici
di varia natura, simmetrici ed asimmetrici, enolizzabili e non, achirali prochirali e chirali prochirali
enantiopur
Unlocking Access to Enantiopure Fused Uracils by Chemodivergent [4+2] CrossâCycloadditions: DFTâSupported HomoâSynergistic Organocatalytic Approach
The discovery of chemical methods enabling the construction of carbocycleâfused uracils which embody a threeâdimensional and functionalâgroupârich architecture is a useful tool in medicinal chemistry oriented synthesis. In this work, an unprecedented amineâcatalyzed [4+2] crossâcycloaddition is documented; it involves remotely enolizable 6âmethyluracilâ5âcarbaldehydes and ÎČâaryl enals, and chemoselectively produces two novel bicyclic and tricyclic fused uracil chemotypes in good yields with a maximum level of enantiocontrol. Inâdepth mechanistic investigations and control experiments support an intriguing homoâsynergistic organocatalytic approach, where the same amine organocatalyst concomitantly engages both aldehyde partners in a stepwise eliminative [4+2] cycloaddition, whose vinylogous iminium ion intermediate product may divergeâdepending upon conditionsâto either bicyclic targets by hydrolysis or tricyclic products by a second homoâsynergistic trienamineâmediated stepwise [4+2] cycloaddition
Direct vinylogous Michael addition of prochiral 3-alkylideneoxindoles to nitroolefins
3-Alkylidene-2-oxindoles represent a simple, yet enabling subfamily of indole alkaloids, and their ability to react as electron-poor acceptors has largely been investigated. In contrast, their utility as pronucleophilic synthons remains elusive. In this context, the present describes the successful execution of the direct, organocatalytic
asymmetric Michael addition of prochiral 3-alkylideneoxindoles to nitroolefins
Sintesi di nuove strutture macrocicliche a ridotta libertĂ conformazionale
L'obiettivo della nostra ricerca consiste nella creazione di nuove strutture macrocicliche a
ridotta libertĂ conformazionale che incorporino la sequenza consensus RGD per mezzo di
una funzione Îł-amminoacidica supportata da anelli ciclopentanici (Acpca), ossidrilati e
non. Tali scaffold amminoacidici possono essere visti di fatto come mimetici dellâacido Îł-
amminobutanoico bloccato in una conformazione a W da un ponte α,γ-etilene o
idrossietilene. La valutazione biologica in vitro dei ciclo-pseudopeptidi
mediante test di binding verso i recettori αvÎČ3 e αvÎČ5 isolati, lâapprofondito studio
strutturale in soluzione via NMR e, infine, studi di docking eseguiti sulla struttura a raggi X
del segmento extracellulare dellâintegrina αvÎČ3 complessata con il composto di riferimento
EMD121974 hanno completato il nostro studio
Synthesis of 1-(2-hydroxyaryl)-1,2,3-propanetriol and 1-(2-hydroxyaryl)-2-amino-1,3-propanediol derivatives of either threo or erythro configuration
The Vinylogous Aldol Reaction:Â A Valuable, Yet Understated CarbonâCarbon Bond-Forming Maneuver
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