2-(Trialkylsilyl)aryl trifluoromethanesulfonates as aryne precursors in the development of methodologies for obtaining nitrogen-containing heterocyclic compounds and total syntheses of bioactive natural products

• Grant number: 17/21990-0
• Support Opportunities: Regular Research Grants
• Start date: February 01, 2018
• End date: January 31, 2020
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Organic Chemistry
• Principal Investigator: Cristiano Raminelli
• Grantee: Cristiano Raminelli
• Host Institution: Instituto de Ciências Ambientais, Químicas e Farmacêuticas (ICAQF). Universidade Federal de São Paulo (UNIFESP). Campus Diadema. Diadema , SP, Brazil

Abstract

The benzyne chemistry has found applications in organic chemistry, including total syntheses of natural products and preparations of functional materials. In this sense, 2-(trimethylsilyl)aryl trifluoromethanesulfonates emerge as an important alternative for the formation of benzyne and derivatives, under mild reaction conditions, enlarging the scope of benzyne chemistry applications in preparative organic chemistry. In this context, we aim to develop a synthetic route that employs organometallic catalysis, avoiding the use of n-butyllithium, a strongly basic and nucleophilic reagent, in the preparation of functionalized 2-(triethylsilyl)aryl triflates. In addition, we intend to use 2-(trimethylsilyl)aryl triflates in the development of methodologies to obtain nitrogen-containing heterocyclic compounds, namely, isoquinolines and dehydroaporphines, and in total syntheses of bioactive natural products, including three non-chiral anthraquinones, represented by morindaparvin A, as well as two protoberberine alkaloids, (S)-tetrahydropalmatine and (+)-coridaline, and one aporphine alkaloid, (S)-nuciferine, exploring enantioselective hydrogenations as approach for the introduction of chirality. (AU)

Scientific publications

(5)

(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)

MURACA, ANA CAROLINA A.; RAMINELLI, CRISTIANO. Exploring Possible Surrogates for Kobayashi's Aryne Precursors. ACS OMEGA, v. 5, n. 5, p. 2440-2457, FEB 11 2020. (16/10894-7, 17/21990-0)

CORREA, BIANCA K.; SILVA, TAMIRIS R. C.; RAMINELLI, CRISTIANO. Total syntheses of (+)-bernumidine and its unnatural enantiomer. Tetrahedron Letters, v. 59, n. 39, p. 3583-3585, SEP 26 2018. (17/21990-0)

CORREA, BIANCA K.; SILVA, TAMIRIS R. C.; RAMINELLI, CRISTIANO. Total syntheses of (+)-bernumidine and its unnatural enantiomer. Clinica Chimica Acta, v. 485, p. 3583-3585, OCT 2018. (17/21990-0)

ROCHA, BEATRIZ C. O.; PERECIM, GIVAGO P.; RAMINELLI, CRISTIANO. Biomimetic Iodofunctionalization of Aromatic and Heteroaromatic Compounds Catalyzed by Selenium Tetrachloride. SYNOPEN, v. 3, n. 4, p. 142-147, OCT 2019. (17/21990-0)

PERECIM, GIVAGO P.; DEFLON, VICTOR M.; MARTINS, GABRIEL R.; PINTO, LEANDRO M. C.; CASAGRANDE, GLEISON A.; OLIVEIRA-SILVA, DIOGO; RAMINELLI, CRISTIANO. Stereoselective total synthesis of (S)- and (R)-nuciferine using benzyne chemistry. Tetrahedron, v. 76, n. 38, SEP 18 2020. (09/54011-8, 17/21990-0)