12 research outputs found
Sonochemical synthesis of bis(tri-n-butylstannyl) aromatic compounds via Barbier-like reactions
This paper reports a study of the synthesis of aryltri-n-butylstannanes via a sonochemical Barbier reaction of aryl- and heteroaryl bromides with bis(tri-n-butyltin) oxide (2) in THF. Our results demonstrate that, despite previous reports on contrary, the aryltributylstannanes can also be obtained under the same reaction conditions via sonicated reactions between aryl monobromides and tri-nbutyltin chloride (2). A comparative study of the reactions of electrophiles 2 and 3 with bromobenzene, 2-bromopyridin, o- and m-bromoanisole, m-bromotoluene, 9-bromophenthrene, and 9-bromoanthracene, indicates that the corresponding aryl- and heteroaryl-tri-n-butylstannyl derivatives are obtained in about the same yields. Best reaction conditions and the results obtained in the investigation of the sonicated reactions between several aromatic and heteroaromatic dibromides are also reported. It was found that the reactions using 1,2-, 1,3-, and 1,4-dibromobenzenes, 4,40-dibromobiphenyl, 1,4-dibromonaphthalene, 2,5- and 3,5-dibromopyridines, and 2,5-dibromothiophene lead to the corresponding bis(tri-n-butylstannylated) derivatives in many cases in very high yields. Also the excellent results obtained in the sonicated reactions of 1,3,5-tribromobenzene with 2 and 3 are reported.Fil: Gerbino, DarĂo CĂ©sar. Consejo Nacional de Investigaciones CientĂficas y TĂ©cnicas. Centro CientĂfico TecnolĂłgico BahĂa Blanca. Instituto de QuĂmica del Sur; Argentina. Universidad Nacional del Sur; ArgentinaFil: Fidelibus, Pablo Martin. Consejo Nacional de Investigaciones CientĂficas y TĂ©cnicas. Centro CientĂfico TecnolĂłgico BahĂa Blanca. Instituto de QuĂmica del Sur; Argentina. Universidad Nacional del Sur; ArgentinaFil: Mandolesi, Sandra Delia. Consejo Nacional de Investigaciones CientĂficas y TĂ©cnicas. Centro CientĂfico TecnolĂłgico BahĂa Blanca. Instituto de QuĂmica del Sur; Argentina. Universidad Nacional del Sur; ArgentinaFil: Ocampo, Romina Andrea. Consejo Nacional de Investigaciones CientĂficas y TĂ©cnicas. Centro CientĂfico TecnolĂłgico BahĂa Blanca. Instituto de QuĂmica del Sur; Argentina. Universidad Nacional del Sur; ArgentinaFil: Scoccia, Jimena. Consejo Nacional de Investigaciones CientĂficas y TĂ©cnicas. Centro CientĂfico TecnolĂłgico BahĂa Blanca. Instituto de QuĂmica del Sur; Argentina. Universidad Nacional del Sur; ArgentinaFil: PodestĂĄ, Julio Cesar. Consejo Nacional de Investigaciones CientĂficas y TĂ©cnicas. Centro CientĂfico TecnolĂłgico BahĂa Blanca. Instituto de QuĂmica del Sur; Argentina. Universidad Nacional del Sur; Argentin
Hydrogen sulphide-triggered theranostic prodrugs based on the dynamic chemistry of tetrazines
[EN] Dynamic nucleophilic aromatic substitution of tetrazines (S(N)Tz) has been employed to build theranostic prodrugs that are activated by hydrogen sulfide. H2S is typically found in high concentrations in some kinds of cancer cells and it is able to trigger the disassembly of tetrazine prodrugs. In such a way, a dual release of drugs and/or fluorescent compounds can be selectively triggered.This work was financially supported by Ministerio de Ciencia e InnovaciĂłn (PGC2018-094503-B-C21). J.S. thanks Cabildo de Tenerife for the AgustĂn de Betancourt programme. M.D.P thanks the ACIISI and the European Social Fund (ESF) for a predoctoral grant
Direct Access to 2,3,4,6-Tetrasubstituted Tetrahydro-2H-pyrans via Tandem SN2'-Prins Cyclization
A new direct and diastereoselective synthesis of activated 2,3,4,6-tetrasubstituted tetrahydro-2H-pyrans is described. In this reaction iron(III) catalyzed an SN2â-Prins cyclization tandem process leading to the creation of three new stereocenters in one single step. These activated tetrahydro-2H-pyran units are easily derivatizable through CuAAC conjugations in order to generate multi-functionalized complex molecules. DFT calculations support the in situ SN2â reaction as a preliminary step in the Prins cyclizatio
Synthesis of organotin derivatives of optically active eleven-membered macrodiolides
The synthesis and the results obtained in the hydrostannation of eight new TADDOL diacrylates and methacrylates are reported. The addition of triorganotin hydrides, R3SnH, 12-14 (R = nBu, neophyl, Ph, respectively) to diesters 6-11 containing different combinations of substituents at the C-2 carbon of the dioxolane ring, led to macrocyclization products in all cases. The cyclohydrostannation of diacrylate 10 proceeded with complete diastereoselectivity. The cyclohydrostannation of diesters 33 and 34 with hydrides 12 and 14 in all cases only afforded one stannylated macrocycle.Fil: Scoccia, Jimena. Consejo Nacional de Investigaciones CientĂficas y TĂ©cnicas. Centro CientĂfico TecnolĂłgico Conicet - BahĂa Blanca. Instituto de QuĂmica del Sur. Universidad Nacional del Sur. Departamento de QuĂmica. Instituto de QuĂmica del Sur; ArgentinaFil: Gerbino, DarĂo CĂ©sar. Consejo Nacional de Investigaciones CientĂficas y TĂ©cnicas. Centro CientĂfico TecnolĂłgico Conicet - BahĂa Blanca. Instituto de QuĂmica del Sur. Universidad Nacional del Sur. Departamento de QuĂmica. Instituto de QuĂmica del Sur; ArgentinaFil: PodestĂĄ, Julio Cesar. Consejo Nacional de Investigaciones CientĂficas y TĂ©cnicas. Centro CientĂfico TecnolĂłgico Conicet - BahĂa Blanca. Instituto de QuĂmica del Sur. Universidad Nacional del Sur. Departamento de QuĂmica. Instituto de QuĂmica del Sur; Argentin
Synthesis of Tetrasubstituted Tetrahydropyrans by a tandem SN2Âż-Prins Cyclization
Trabajo presentado en la XXVI ReuniĂłn Bienal de QuĂmica OrgĂĄnica de la Real Sociedad Española de QuĂmica, celebrada en Punta UmbrĂa, Huelva (España) del 14 al 17 de junio de 2016.The tetrahydropyrans are common structural units present and widespread in the natural products. These products have powerful bioactivity against many disease.[1] Therefore, the development of new and sustainable methodologies allowing the efficient access to these oxacycles represents a target, as well as a challenge far synthetic organic chemists. [2] In this work, we shall show the tandem SN2 '-Prins cyclization of chloroallyl bis-homoallyl alcohols catalyzed by iron(lll) salts, that lead to tetrasubstituted tetrahydropyrans with total diastereoselectivity (Scheme 1).We thank the Spanish MINECO, co-financed by the European Regional Development Fund (ERDF), CTQ2014-56362-C2-1-P for financiaL support. S. J. P. thanks the Ministerio de EducaciĂłn, Cultura y Deporte far a FPU fellowship.Peer Reviewe
Stereoselective synthesis and some properties of new chlorodiorganotin- substituted macrodiolides
Radical tandem addition of dialkyltin chlorohydrides, R2SnHCl (R = n-Bu, neophyl, Ph), to TADDOL's substituted diacrylates (47) led to the corresponding products of cyclohydrostannation. The new optically active chlorodialkyltinsubstituted 11-membered macrodiolides were obtained in very good yields and with much higher stereoselectivity than that achieved with the corresponding monohydrides, R3SnH. Thus, the cyclohydrostannation of diacrylate 4 and dimethacrylate 5 lead to just one diastereomer in the first case and to an easily separable mixture of two diastereomers in the second. Reduction of the new organotin macrocycles with LiAlH4 afforded optically active organotin derivatives structurally related to glutaric acid. Oxidation of the new chlorodiorganotin-substituted macrocycles with 30% hydrogen peroxide gave the new 11-membered macrocycles 30 and 31 free of tin in an average total yield of 43.4% from TADDOL. Full 1H, 13C, and 119Sn data are also reported. © 2012 American Chemical Society.Fil: Gerbino, DarĂo CĂ©sar. Consejo Nacional de Investigaciones CientĂficas y TĂ©cnicas. Centro CientĂfico TecnolĂłgico Conicet - BahĂa Blanca. Instituto de QuĂmica del Sur. Universidad Nacional del Sur. Departamento de QuĂmica. Instituto de QuĂmica del Sur; ArgentinaFil: Scoccia, Jimena. Consejo Nacional de Investigaciones CientĂficas y TĂ©cnicas. Centro CientĂfico TecnolĂłgico Conicet - BahĂa Blanca. Instituto de QuĂmica del Sur. Universidad Nacional del Sur. Departamento de QuĂmica. Instituto de QuĂmica del Sur; ArgentinaFil: Koll, Liliana Cristina. Consejo Nacional de Investigaciones CientĂficas y TĂ©cnicas. Centro CientĂfico TecnolĂłgico Conicet - BahĂa Blanca. Instituto de QuĂmica del Sur. Universidad Nacional del Sur. Departamento de QuĂmica. Instituto de QuĂmica del Sur; ArgentinaFil: Mandolesi, Sandra Delia. Universidad Nacional del Sur. Departamento de QuĂmica; ArgentinaFil: PodestĂĄ, Julio Cesar. Consejo Nacional de Investigaciones CientĂficas y TĂ©cnicas. Centro CientĂfico TecnolĂłgico Conicet - BahĂa Blanca. Instituto de QuĂmica del Sur. Universidad Nacional del Sur. Departamento de QuĂmica. Instituto de QuĂmica del Sur; Argentin
Sustainable oxidations with air mediated by gallic acid: Potential applicability in the reutilization of grape pomace
Gallic acid converts atmospheric oxygen into hydrogen peroxide, which is able to oxidize arylboronic acids as a proof of concept of sustainable oxidations. Moreover, tannic acid and grape pomace extract are also able to perform oxidations with air. Therefore this work unleashes an alternative method for reutilization and valorization of bio-wastes rich in tannins.Fil: Scoccia, Jimena. Consejo Nacional de Investigaciones CientĂficas y TĂ©cnicas. Centro CientĂfico TecnolĂłgico Conicet - BahĂa Blanca. Instituto de QuĂmica del Sur. Universidad Nacional del Sur. Departamento de QuĂmica. Instituto de QuĂmica del Sur; ArgentinaFil: Perretti, Marcelle D.. Universidad de la Laguna. Departamento de QuĂmica OrgĂĄnica. Instituto Universitario de Bio-OrgĂĄnica "Antonio GonzĂĄlez"; EspañaFil: MonzĂłn, Diego M.. Universidad de la Laguna. Departamento de QuĂmica OrgĂĄnica. Instituto Universitario de Bio-OrgĂĄnica "Antonio GonzĂĄlez"; EspañaFil: CrisĂłstomo, Fernando P.. Universidad de la Laguna. Departamento de QuĂmica OrgĂĄnica. Instituto Universitario de Bio-OrgĂĄnica "Antonio GonzĂĄlez"; EspañaFil: MartĂn GarcĂa, Victor Sotero. Universidad de la Laguna. Departamento de QuĂmica OrgĂĄnica. Instituto Universitario de Bio-OrgĂĄnica "Antonio GonzĂĄlez"; EspañaFil: Carrillo, Romen. Universidad de la Laguna. Departamento de QuĂmica OrgĂĄnica. Instituto Universitario de Bio-OrgĂĄnica "Antonio GonzĂĄlez"; Españ
Iron(II) promoted direct synthesis of dibenzo[ b,e ]oxepin-11(6H)-one derivatives with biological activity. A short synthesis of doxepin
A novel and efficient synthesis of dibenzo[b,e]oxepin-11(6H)-ones by direct intramolecular ortho-acylation from readily available 2-(phenoxymethyl)benzoic acids was developed. The method takes advantage of a newly developed cooperative system consisting of sustainable FeCl2 and Cl2CHOCH3 as the key components. This methodology is compatible with a wide variety of functional groups in good to excellent yields and high regioselectivity. The synthetic application of new protocol was extended to the synthesis of known tricyclic drug doxepin as well as a small library of oxepin based derivatives. For the first time, the obtained dibenzo[b,e]oxepinone derivatives were evaluated for their biological activities on the free-living nematode Caenorhabditis elegans as an effective and cost-efficient model system for anthelmintic discovery.Fil: Scoccia, Jimena. Consejo Nacional de Investigaciones CientĂficas y TĂ©cnicas. Centro CientĂfico TecnolĂłgico Conicet - BahĂa Blanca. Instituto de QuĂmica del Sur. Universidad Nacional del Sur. Departamento de QuĂmica. Instituto de QuĂmica del Sur; ArgentinaFil: Castro, Maria Julia. Consejo Nacional de Investigaciones CientĂficas y TĂ©cnicas. Centro CientĂfico TecnolĂłgico Conicet - BahĂa Blanca. Instituto de Investigaciones BioquĂmicas de BahĂa Blanca. Universidad Nacional del Sur. Instituto de Investigaciones BioquĂmicas de BahĂa Blanca; Argentina. Consejo Nacional de Investigaciones CientĂficas y TĂ©cnicas. Centro CientĂfico TecnolĂłgico Conicet - BahĂa Blanca. Instituto de QuĂmica del Sur. Universidad Nacional del Sur. Departamento de QuĂmica. Instituto de QuĂmica del Sur; ArgentinaFil: Faraoni, MarĂa BelĂ©n. Consejo Nacional de Investigaciones CientĂficas y TĂ©cnicas. Centro CientĂfico TecnolĂłgico Conicet - BahĂa Blanca. Instituto de QuĂmica del Sur. Universidad Nacional del Sur. Departamento de QuĂmica. Instituto de QuĂmica del Sur; ArgentinaFil: Bouzat, Cecilia Beatriz. Consejo Nacional de Investigaciones CientĂficas y TĂ©cnicas. Centro CientĂfico TecnolĂłgico Conicet - BahĂa Blanca. Instituto de Investigaciones BioquĂmicas de BahĂa Blanca. Universidad Nacional del Sur. Instituto de Investigaciones BioquĂmicas de BahĂa Blanca; ArgentinaFil: MartĂn GarcĂa, Victor Sotero. Universidad de La Laguna; EspañaFil: Gerbino, DarĂo CĂ©sar. Consejo Nacional de Investigaciones CientĂficas y TĂ©cnicas. Centro CientĂfico TecnolĂłgico Conicet - BahĂa Blanca. Instituto de QuĂmica del Sur. Universidad Nacional del Sur. Departamento de QuĂmica. Instituto de QuĂmica del Sur; Argentin
Stereoselective Synthesis and Some Properties of New Chlorodiorganotin-Substituted Macrodiolides
Radical tandem addition of dialkyltin chlorohydrides,
R<sub>2</sub>SnHCl (R = <i>n</i>-Bu, neophyl, Ph), to TADDOLâs
substituted diacrylates (<b>4</b>â<b>7</b>) led
to the corresponding products of cyclohydrostannation. The new optically
active chlorodialkyltin-substituted 11-membered macrodiolides were
obtained in very good yields and with much higher stereoselectivity
than that achieved with the corresponding monohydrides, R<sub>3</sub>SnH. Thus, the cyclohydrostannation of diacrylate <b>4</b> and
dimethacrylate <b>5</b> lead to just one diastereomer in the
first case and to an easily separable mixture of two diastereomers
in the second. Reduction of the new organotin macrocycles with LiAlH<sub>4</sub> afforded optically active organotin derivatives structurally
related to glutaric acid. Oxidation of the new chlorodiorganotin-substituted
macrocycles with 30% hydrogen peroxide gave the new 11-membered macrocycles <b>30</b> and <b>31</b> free of tin in an average total yield
of 43.4% from TADDOL. Full <sup>1</sup>H, <sup>13</sup>C, and <sup>119</sup>Sn data are also reported
Efficient asymmetric TADDOLs-organocatalyzed cycloaddition for the synthesis of allyltin derivatives
We report here the results obtained in the study of organocatalytic asymmetric DielsâAlder reactions to optimize the synthesis of stereo defined allyltin derivatives using (Z)-2-(1-cyclohexenyl)-1-ethenyl(trineophyl)stannane (1) as diene and substituted dienophiles in the presence of (4R,5R)-α,α,αâČ,αâČ-tetraphenyl-1,3-dioxolane-4,5-dimethanol (TADDOL, I) and analogs (4R,5R)-α,α,αâČ,αâČ-tetra(1-naphtyl)-1,3-dioxolane-4,5-dimethanol (II) and (4R,5R)-α,α,αâČ,αâČ-tetra(9-phenantryl)1,3-dioxolane-4,5-dimethanol (III) as chiral catalysts to enhance stereoselectivity through hydrogen bond activation of the dienophile. Catalyst II provided excellent results and ultrasonic radiation at low temperature showed the shorter reaction times.Fil: Ocampo, Romina Andrea. Consejo Nacional de Investigaciones CientĂficas y TĂ©cnicas. Centro CientĂfico TecnolĂłgico Conicet - BahĂa Blanca. Instituto de QuĂmica del Sur. Universidad Nacional del Sur. Departamento de QuĂmica. Instituto de QuĂmica del Sur; ArgentinaFil: Scoccia, Jimena. Consejo Nacional de Investigaciones CientĂficas y TĂ©cnicas. Centro CientĂfico TecnolĂłgico Conicet - BahĂa Blanca. Instituto de QuĂmica del Sur. Universidad Nacional del Sur. Departamento de QuĂmica. Instituto de QuĂmica del Sur; ArgentinaFil: Costantino, Andrea Rosana. Consejo Nacional de Investigaciones CientĂficas y TĂ©cnicas. Centro CientĂfico TecnolĂłgico Conicet - BahĂa Blanca. Instituto de QuĂmica del Sur. Universidad Nacional del Sur. Departamento de QuĂmica. Instituto de QuĂmica del Sur; ArgentinaFil: Montiel Schneider, MarĂa Gabriela. Consejo Nacional de Investigaciones CientĂficas y TĂ©cnicas. Centro CientĂfico TecnolĂłgico Conicet - BahĂa Blanca. Instituto de QuĂmica del Sur. Universidad Nacional del Sur. Departamento de QuĂmica. Instituto de QuĂmica del Sur; ArgentinaFil: Gerbino, DarĂo CĂ©sar. Consejo Nacional de Investigaciones CientĂficas y TĂ©cnicas. Centro CientĂfico TecnolĂłgico Conicet - BahĂa Blanca. Instituto de QuĂmica del Sur. Universidad Nacional del Sur. Departamento de QuĂmica. Instituto de QuĂmica del Sur; ArgentinaFil: Zuñiga, Adriana Elena. Consejo Nacional de Investigaciones CientĂficas y TĂ©cnicas. Centro CientĂfico TecnolĂłgico Conicet - BahĂa Blanca. Instituto de QuĂmica del Sur. Universidad Nacional del Sur. Departamento de QuĂmica. Instituto de QuĂmica del Sur; ArgentinaFil: Pereyra, Marcelo Tomas. Consejo Nacional de Investigaciones CientĂficas y TĂ©cnicas. Centro CientĂfico TecnolĂłgico Conicet - BahĂa Blanca. Instituto de QuĂmica del Sur. Universidad Nacional del Sur. Departamento de QuĂmica. Instituto de QuĂmica del Sur; ArgentinaFil: Koll, Liliana Cristina. Consejo Nacional de Investigaciones CientĂficas y TĂ©cnicas. Centro CientĂfico TecnolĂłgico Conicet - BahĂa Blanca. Instituto de QuĂmica del Sur. Universidad Nacional del Sur. Departamento de QuĂmica. Instituto de QuĂmica del Sur; ArgentinaFil: Mandolesi, Sandra Delia. Consejo Nacional de Investigaciones CientĂficas y TĂ©cnicas. Centro CientĂfico TecnolĂłgico Conicet - BahĂa Blanca. Instituto de QuĂmica del Sur. Universidad Nacional del Sur. Departamento de QuĂmica. Instituto de QuĂmica del Sur; Argentin