New approaches in asymmetric synthesis of tetrahydrofuran and tetrahydropyran-derivatives with potential application in the preparation of bioactive molecules

• Grant number: 13/02311-3
• Support Opportunities: Regular Research Grants
• Start date: May 01, 2013
• End date: October 31, 2015
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Organic Chemistry
• Principal Investigator: Marco Antonio Barbosa Ferreira
• Grantee: Marco Antonio Barbosa Ferreira
• Host Institution: Centro de Ciências Exatas e de Tecnologia (CCET). Universidade Federal de São Carlos (UFSCAR). São Carlos , SP, Brazil

Abstract

The incredible number of bioactive natural products containing tetrahydrofuran (THF) and tetrahydropyran derivatives (THP) have been driven the development of new methods of preparing functionalized cyclic ethers. This research project will focus on the development and application of new synthetic methodologies involving the preparation of substituted cyclic ethers for the synthesis of natural products and bioactive molecules. One of the research topics deals with cobalt-catalyzed asymmetric cascade aerobic oxidative-cyclization/ radical-cyclization reactions. This reaction employs a low cost metal catalyst, showing low toxicity, broad access, performed in PA grade solvents in an open system using molecular oxygen as the oxidant, and with high tolerance to functional groups. This reaction generates a radical, allowing further functionalization through cascade reactions that will add structural complexity in just one step. An intramolecular versions will be investigated and will provide highly functionalized-tetrahydrofuran derivatives. In addition, we aim to provide further evidences on the nature of this transformation by theoretical calculations. In other shaft work, we intend to develop a new synthetic methodology allowing quick access to trisubstituted-THP, with special attention to 2,6-cis and 2,6-trans relations, employing epoxy-diols via one pot and cascade reactions. To this end, studies on the asymmetric synthesis of epoxy-diols from aldol adducts obtained by 1,5-diastereoselective aldol reactions will be performed. (AU)

Scientific publications

(11)

(References retrieved automatically from Web of Science and SciELO through information on FAPESP grants and their corresponding numbers as mentioned in the publications by the authors)

ALI, SAJJAD; MILANEZI, HENRIQUE; ALVES, TANIA M. F.; TORMENA, CLAUDIO FRANCISCO; FERREIRE, MARCO A. B.. Cobalt-Catalyzed Stereoselective Synthesis of 2,5-trans-THF Nitrile Derivatives as a Platform for Diversification: Development and Mechanistic Studies. Journal of Organic Chemistry, v. 83, n. 15, p. 7694-7713, AUG 3 2018. (13/02311-3, 15/08541-6, 14/50249-8)

VILLARREAL, WILMER; COLINA-VEGAS, LEGNA; DE OLIVEIRA, CLAYTON RODRIGUES; TENORIO, JUAN C.; ELLENA, JAVIER; GOZZO, FABIO C.; COMINETTI, MARCIA REGINA; FERREIRA, ANTONIO G.; BARBOSA FERREIRA, MARCO ANTONIO; NAVARRO, MARIBEL; et al. Chiral Platinum(II) Complexes Featuring Phosphine and Chloroquine Ligands as Cytotoxic and Monofunctional DNA-Binding Agents. Inorganic Chemistry, v. 54, n. 24, p. 11709-11720, DEC 21 2015. (13/02311-3)

DE ASSIS, FRANCISCO F.; FERREIRA, MARCO A. B.; BROCKSOM, TIMOTHY J.; DE OLIVEIRA, KLEBER T.. NIR bacteriochlorin chromophores accessed by Heck and Sonogashira cross-coupling reactions on a tetrabromobacteriochlorin derivative. ORGANIC & BIOMOLECULAR CHEMISTRY, v. 14, n. 4, p. 1402-1412, 2016. (11/13993-2, 13/02311-3, 13/06532-4, 12/24096-4)

ALVES, TANIA M. F.; COSTA, MATEUS O.; BISPO, BEATRIZ A. D.; PEDROSA, FABIANA L.; FERREIRA, MARCO A. B.. Cobalt-catalyzed oxidative cyclization of gem-disubstituted conjugated alkenols. Tetrahedron Letters, v. 57, n. 30, p. 3334-3338, JUL 27 2016. (13/02311-3)

ULIANA, MARCIANA P.; SERVILHA, BRUNO M.; ALEXOPOULOS, OLGA; DE OLIVEIRA, KLEBER T.; TORMENA, CLAUDIO F.; FERREIRA, MARCO A. B.; BROCKSOM, TIMOTHY J.. The Diels-Alder reactions of para-benzoquinone nitrogen-derivatives: an experimental and theoretical study. Tetrahedron, v. 70, n. 39, p. 6963-6973, SEP 30 2014. (11/13993-2, 13/02311-3, 13/06532-4)

ALI, AKBAR; CORREA, ARLENE G.; ALVES, DIEGO; ZUKERMAN-SCHPECTOR, JULIO; WESTERMANN, BERNHARD; FERREIRA, MARCO A. B.; PAIXAO, MARCIO W.. An efficient one-pot strategy for the highly regioselective metal-free synthesis of 1,4-disubstituted-1,2,3-triazoles. CHEMICAL COMMUNICATIONS, v. 50, n. 80, p. 11926-11929, 2014. (13/02311-3, 09/54040-8, 09/07281-0)

AIMOLA, TULIO J.; LIMA, DIMAS J. P.; DIAS, LUIZ C.; TORMENA, CLAUDIO F.; FERREIRA, MARCO A. B.. H-1 chemical shift differences of Prelog-Djerassi lactone derivatives: DFT and NMR conformational studies. ORGANIC & BIOMOLECULAR CHEMISTRY, v. 13, n. 7, p. 2140-2145, 2015. (13/02311-3)

FERREIRA, MARCO A. B.; DIAS, LUIZ C.; LEONARCZYK, IVES A.; POLO, ELLEN C.; DE LUCCA, JR., EMILIO C.. Exploring the Aldol Reaction in the Synthesis of Bioactive Compounds. CURRENT ORGANIC SYNTHESIS, v. 12, n. 5, p. 547-564, 2015. (11/06722-2, 11/06721-6, 13/02311-3, 12/02230-0)

DE OLIVEIRA, KLEBER T.; MOMO, PATRICIA B.; DE ASSIS, FRANCISCO F.; FERREIRA, MARCO A. B.; BROCKSOM, TIMOTHY J.. Chlorins: Natural Sources, Synthetic Developments and Main Applications. CURRENT ORGANIC SYNTHESIS, v. 11, n. 1, p. 42-58, FEB 2014. (11/13993-2, 13/02311-3, 13/06532-4, 12/04964-1)

YEO, CHIEN ING; HALIM, SITI NADIAH ABDUL; NG, SEIK WENG; TAN, SENG LIM; ZUKERMAN-SCHPECTOR, JULIO; FERREIRA, MARCO A. B.; TIEKINK, EDWARD R. T.. Investigation of putative arene-C-H center dot center dot center dot pi(quasi-chelate ring) interactions in copper(I) crystal structures. CHEMICAL COMMUNICATIONS, v. 50, n. 45, p. 5984-5986, 2014. (13/02311-3)

DE LA TORRE, ALEXANDER F.; RIVERA, DANIEL G.; FERREIRA, MARCO A. B.; CORREA, ARLENE G.; PAIXAO, MARCIO W.. Multicomponent Combinatorial Development and Conformational Analysis of Prolyl Peptide-Peptoid Hybrid Catalysts: Application in the Direct Asymmetric Michael Addition. Journal of Organic Chemistry, v. 78, n. 20, p. 10221-10232, OCT 18 2013. (13/02311-3, 09/07281-0)