Photocatalyzed reductive fluoroalkylation of 2-acetoxyglycals towards the stereoselective synthesis of α-1-fluoroalkyl-: C -glycosyl derivatives

A benign, efficient, regio- and stereoselective protocol for the syntheses of α-1-fluoroalkyl-C-glycosyl compounds bearing CF3, C4F9, and C6F13 substituents on the anomeric carbon has been developed by a new methodology starting from 2-acetoxyglycals for the first time. Remarkably, the reactions proceeded in only one step, through the visible light-photocatalyzed reductive fluoroalkylation of 2-acetoxyglycals by means of an Ir photocatalyst and employed commercially available fluoroalkyl iodides n-CnF2n+1-I (n = 1, 4, 6) as a source of fluoroalkyl radicals.Fil: Mora Flores, Erwin Wilfredo. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Orgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay; ArgentinaFil: Uhrig, Maria Laura. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; ArgentinaFil: Postigo, Jose Alberto. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Orgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay; Argentin

The Role of Photocatalysts in Radical Chains of Homolytic Aromatic Substitutions, Radical Addition to Olefins, and Nucleophilic Radical Substitution Mechanisms

Photoinitiated perfluorobutylation reactions of 2-anisidine 1, propenyloxybenzene 2, and 2-mercaptoethanol 3 have been carried out employing commercially available n-C4F9I as the source of C4F9 radicals under three different photocatalysts (PCs) absorbing in the violet (Ir[dF(CF3)ppy]2(dtbbpy)+ (PC-1)), green (Rose Bengal (PC-2)) and red (zinc phthalocyanine PhZn (PC-3)) regions of the electromagnetic spectrum, in order to explore the quantum yields and radical chain lengths for each type of transformation and photoinitiated system. For substrates 1-3 and their different types of reactions, the comparative study between PCs seeks to establish the extent to which regioproducts, yields, and mechanistic proposals are influenced by the intervention of each PC. The different overall quantum yields and chain lengths obtained for each type of reaction under each PC are a direct consequence of the efficiency of the photoinitiation events, i.e., primary radical production, propagation and termination steps. This will have important implications in the understanding and representations of the mechanisms postulated, in terms of closed and open catalytic cycles. One strategy we apply to uncover radical propagating chains in our mechanisms is to explore photocatalysts that operate in oxidative and reductive quenching manners for each type of transformation.Fil: Yerien, Damián Emilio. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay; ArgentinaFil: Barata Vallejo, Sebastian. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay; Argentina. Centre National de la Recherche Scientifique; FranciaFil: Mora Flores, Erwin Wilfredo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay; Argentina. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; ArgentinaFil: Postigo, Jose Alberto. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay; Argentin

Approaches to the Synthesis of Perfluoroalkyl-Modified Carbohydrates and Derivatives: Thiosugars, Iminosugars, and Tetrahydro(thio)pyrans

Fluoroalkyl-substituted carbohydrates play relevant roles in diverse areas such as supramolecular chemistry, glycoconjugation, liquid crystals, and surfactants, with direct applications as wetting, antifreeze, and coating agents. In light of these promising applications, new methodologies for the late-stage incorporation of fluoroalkyl RF groups into carbohydrates and derivatives are herein presented as they are relevant to the synthetic carbohydrate community. Previously reviewed protocols for the installation of RF groups onto carbohydrates and derivatives will be succinctly summarized in the light of the new achievements. Fluoroalkyl-substituted iminosugars, on the other hand, are also interesting glycomimetic derivatives with prominent roles as glycosidases and glycosyltransferases inhibitors, as has recently been demonstrated. Also, they positively contribute to the study of sugar–protein interactions and enzyme mechanisms. New advances in the syntheses of fluoroalkyl-substituted iminosugars will also be presented here.Fil: Uhrig, Maria Laura. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Oficina de Coordinacion Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Subsede del Centro de Investigaciones en Hidratos de Carbono | Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono. Subsede del Centro de Investigaciones en Hidratos de Carbono; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; ArgentinaFil: Mora Flores, Erwin Wilfredo. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Orgánica; ArgentinaFil: Postigo, Jose Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Orgánica; Argentin